Fluorochemical composition for treatment of a fibrous substrate

ABSTRACT

The present invention relates to a fluorochemical composition for rendering fibrous substrates oil repellent, water repellent and/or stain or soil repellent. Additionally, the invention also relates to fluorochemical compositions for providing stain release or soil release properties to fibrous substrates. In particular, the present invention relates to fluorochemical compositions that contain a fluorinated polyether compound that can be obtained by reacting an isocyanate component with a particular isocyanate reactive fluorinated polyether compound and a stain release compound. The invention further relates to a method of treating the fibrous substrate with the fluorochemical composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority from U.S. Provisional Application Ser.No. 60/383,392, filed May 24, 2002.

FIELD OF INVENTION

The present invention relates to a fluorochemical composition forrendering fibrous substrates oil repellent, water repellent and/or stainor soil repellent. Additionally, the invention also relates tofluorochemical compositions for providing stain release or soil releaseproperties to fibrous substrates. In particular, the present inventionrelates to fluorochemical compositions that contain a fluorinatedpolyether compound that can be obtained by reacting an isocyanatecomponent with a particular isocyanate reactive fluorinated polyethercompound and a stain release compound. The invention further relates toa method of treating the fibrous substrate with the fluorochemicalcomposition.

BACKGROUND

Compositions for making substrates, in particular fibrous substrates,such as textile, oil- and water repellent have been long known in theart. When treating fibrous substrates and in particular textile such asapparel, it is desired that the textile retains its look and feel asmuch as possible. Therefore, the composition should normally not containcomponents that would affect the look of the product, i.e. the treatmentshould be substantially invisible to the unaided human eye. Also, thefeel of the substrate should preferably be substantially unaffected.Typically this means that only low amounts of the solids of thecomposition can be applied. Accordingly, an oil- and/or water repellentcomposition should be highly effective in rendering a substraterepellent.

Commercially available oil- and/or water repellent compositions aretypically based on fluorinated compounds that have a perfluorinatedaliphatic group. Such compositions are also described in for exampleU.S. Pat. No. 5,276,175 and EP 435 641. The commercial success of thistype of composition can be attributed to their high effectiveness.Fluorinated compounds based on perfluorinated ether moieties have alsobeen described in the prior art for rendering fibrous substrates oil-and/or water repellent. For example, perfluorinated polyether compoundshave been disclosed in EP 1 038 919, EP 273 449, JP-A-04-146917,JP-A-10-081873, U.S. Pat. No. 3,536,710, U.S. Pat. No. 3,814,741, U.S.Pat. No. 3,553,179 and U.S. Pat. No. 3,446,761. It was found thatpreviously disclosed compositions based on perfluorinated polyethercompounds may not be very effective in rendering a fibrous substrateoil- and/or water repellent.

Accordingly, it is a desire to find fluorochemical compositions based ona perfluorinated polyether compound that can provide good to excellentoil- and/or water repellency properties to a fibrous substrate.Preferably, the fluorochemical composition is capable of providingdurable oil- and/or water repellency properties to a fibrous substratesuch that a treated fibrous substrate can substantially maintain therepellency properties even after several washing cycles. Preferably afibrous substrate treated with the fluorochemical composition has a softfeel, preferably the feel of a treated fibrous substrate is either thesame or softer compared to the untreated fibrous substrate. It is afurther desire that the fluorochemical compositions can be easily andefficiently manufactured at a low cost. It is further desired to findcompositions that have environmentally beneficial properties.

SUMMARY OF THE INVENTION

The present invention provides in one aspect a fluorochemicalcomposition comprising a dispersion or a solution of a fluorinatedcompound, wherein said fluorinated compound comprises the reactionproduct of a combination of reactants comprising:

-   -   (i) a fluorinated polyether according to the formula:        R_(f)-Q-T_(k)  (I)    -    wherein R_(f) represents a monovalent perfluorinated polyether        group having a molecular weight of at least 750 g/mol, Q        represents a chemical bond or a divalent or trivalent organic        linking group, T represents a functional group capable of        reacting with an isocyanate and k is 1 or 2;    -   (ii) an isocyanate component selected from a polyisocyanate        compound that has at least 3 isocyanate groups or a mixture of        polyisocyanate compounds wherein the average number of        isocyanate groups per molecule is more than 2; and    -   (iii) optionally one or more co-reactants capable of reacting        with an isocyanate group.

The invention further provides a method of treatment of a fibroussubstrate with the fluorochemical composition whereby oil- and/or waterrepellent properties are provided to the substrate. The fluorochemicalcomposition of the present invention can provide good to excellentrepellency properties to the substrate. Moreover, durable oil- and/orwater repellency properties can be obtained. The fluorochemicalcompositions may further provide soil repellency as well as soil orstain release properties. The term “soil and/or stain release” is usedto mean that a treated substrate that becomes soiled or stained can bemore easily cleaned in for example a home laundering than an untreatedsubstrate that becomes soiled or stained. Soil/stain repellency on theother hand refers to the ability of the treated substrate to repel soilthereby reducing soiling or staining of the substrate.

Generally, the fibrous substrate will retain a soft feel after treatmentwith the fluorochemical composition. Furthermore, the fluorochemicalcomposition is effective even at low levels of application and therepellency properties may be obtained without the need of a heattreatment step.

Also, the fluorochemical compositions of the present inventions aregenerally environmentally friendly in that compositions can be obtainedthat are substantially free of fluorochemical components that eliminateslowly from the body of living organisms. Moreover, it is believed thatfluorochemical degradation products that may form likewise eliminatewell from the body of living organisms. In particular, indications showthat the fluorinated polyether compounds that have a perfluorinatedpolyether moiety having a molecular weight of at least 750 g/mol andperfluorinated polyether degradation products that may form therefromwould eliminate more effectively from the body of living organisms. Inparticular, there are indications that fluorinated polyether compoundshaving a fluorinated polyether moiety derivable from a polycondensationof hexafluoropropylene oxide and having a molecular weight of at least750 g/mol would more effectively eliminate from the body of livingorganisms compared to long chain perfluoroaliphatic compounds.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS OF THE INVENTION

The fluorinated compound used in the fluorochemical composition isobtainable by reacting an isocyanate component and optional co-reactantswith a fluorinated polyether according to formula (I) that has anisocyanate reactive group:R_(f)-Q-T_(k)  (I),wherein R_(f) represents a monovalent perfluorinated polyether group, Qrepresents a chemical bond or a divalent or trivalent non-fluorinatedorganic linking group, T represents a functional group capable ofreacting with an isocyanate and k is 1 or 2.

The perfluorinated polyether moiety R_(f) of the fluorinated polyetherof formula (I) preferably corresponds to the formula:R¹ _(f)—O—R_(f) ²—(R_(f) ³)_(q)—  (II)wherein R¹ _(f) represents a perfluorinated alkyl group, R_(f) ²represents a perfluorinated polyalkyleneoxy group consisting ofperfluorinated alkyleneoxy groups having 1, 2, 3 or 4 carbon atoms or amixture of such perfluorinated alkylene oxy groups, R³ _(f) represents aperfluorinated alkylene group and q is 0 or 1. The perfluorinated alkylgroup R¹ _(f) in formula (II) may be linear or branched and may comprise1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. A typicalperfluorinated alkyl group is CF₃—CF₂—CF₂—. R³ _(f) is a linear orbranched perfluorinated alkylene group that will typically have 1 to 6carbon atoms. For example, R³ _(f) is —CF₂— or —CF(CF₃)—. Examples ofperfluoroalkylene oxy groups of perfluorinated polyalkyleneoxy group R²_(f) include:

—CF₂—CF₂—O—,

—CF(CF₃)—CF₂—O—,

—CF₂—CF(CF₃)—O—,

—CF₂—CF₂—CF₂—O—,

—CF₂—O—,

—CF(CF₃)—O—, and

—CF₂—CF₂—CF₂—CF₂—O.

The perfluoroalkyleneoxy group may be comprised of the sameperfluoroalkylene oxy units or of a mixture of differentperfluoroalkylene oxy units. When the perfluoroalkyleneoxy group iscomposed of different perfluoroalkylene oxy units, they can be presentin a random configuration, alternating configuration or they can bepresent as blocks. Typical examples of perfluorinated polyalkylene oxygroups include:

-   —[CF₂—CF₂—O]_(r)—; —[CF(CF₃)—CF₂—O]_(n)—;    —[CF₂CF₂—O]_(i)—[CF₂O]_(j)— and-   —[CF₂—CF₂—O]_(l)—[CF(CF₃)—CF₂—O]_(m)—; wherein r is an integer of 4    to 25, n is an integer of 3 to 25 and i, l, m and j each are    integers of 2 to 25. A preferred perfluorinated polyether group that    corresponds to formula (II) is    CF₃—CF₂—CF₂—O—[CF(CF₃)—CF₂O]_(n)—CF(CF₃)— wherein n is an integer of    3 to 25. This perfluorinated polyether group has a molecular weight    of 783 when n equals 3 and can be derived from an oligomerization of    hexafluoropropylene oxide. Such perfluorinated polyether groups are    preferred in particular because of their benign environmental    properties.

Examples of linking groups Q include organic groups that comprisearomatic or aliphatic groups that may be interrupted by O, N or S andthat may be substituted, alkylene groups, oxy groups, thio groups,urethane groups, carboxy groups, carbonyl groups, amido groups,oxyalkylene groups, thioalkylene groups, carboxyalkylene and/or anamidoalkylene groups. Examples of functional groups T include thiol,hydroxy and amino groups.

In a particular embodiment, the fluorinated polyether corresponds to thefollowing formula (III):R_(f) ¹—[CF(CF₃)—CF₂O]_(n)—CF(CF₃)-A-Q¹-T_(k)  (III)wherein R_(f) ¹ represents a perfluorinated alkyl group, e.g., a linearor branched perfluorinated alkyl group having 1 to 6 carbon atoms, n isan integer of 3 to 25, A is a carbonyl group or CH₂, Q¹ is a chemicalbond or an organic divalent or trivalent linking group for example asmentioned for the linking group Q above, k is 1 or 2 and T represents anisocyanate reactive group and each T may be the same or different.Particularly preferred compounds are those in which R¹ _(f) representsCF₃CF₂CF₂—. In accordance with a particular embodiment, the moiety-A-Q¹-T_(k) is a moiety of the formula —CO—X—R^(a)(OH)_(k) wherein k is1 or 2, X is O or NR^(b) with R^(b) representing hydrogen or an alkylgroup of 1 to 4 carbon atoms, and R^(a) is an alkylene of 1 to 15 carbonatoms.

Representative examples of the moiety -A-Q¹-T_(k) in above formula (III)include:

-   -   1. —CONR^(c)—CH₂CHOHCH₂OH wherein R^(c) is hydrogen or an alkyl        group of for example 1 to 4 carbon atoms;    -   2. —CONH-1,4-dihydroxyphenyl;    -   3. —CH₂OCH₂CHOHCH₂OH;    -   4. —COOCH₂CHOHCH₂OH; and    -   5. —CONR^(d)—(CH₂)_(m)OH    -    where R^(d) is hydrogen or an alkyl group of 1 to 6 carbons and        m is 2, 3, 4, 6, 8, 10 or 11.

Compounds according to formula (III) can for example be obtained byoligomerization of hexafluoropropylene oxide which results in aperfluoropolyether carbonyl fluoride. This carbonyl fluoride may beconverted into an acid, ester or alcohol by reactions well known tothose skilled in the art. The carbonyl fluoride or acid, ester oralcohol derived therefrom may then be reacted further to introduce thedesired isocyanate reactive groups according to known procedures. Forexample, EP 870 778 describes suitable methods to produce compoundsaccording to formula (III) having desired moieties -A-Q¹-T_(k).Compounds having group 1 listed above can be obtained by reacting themethyl ester derivative of a fluorinated polyether with3-amino-2-hydroxy-propanol. Compounds having the group 5 listed abovecan be obtained in a similar way by reacting with an amino-alcohol thathas only one hydroxy function. For example 2-aminoethanol would yield acompound having the group 5 listed above with R^(d) being hydrogen and mbeing 2.

Still further examples of compounds according to above formula (I) aredisclosed in EP 870 778 or U.S. Pat. No. 3,536,710.

It will be evident to one skilled in the art that a mixture offluorinated polyethers according to formula (I) may be used to preparethe fluorinated polyether compound of the fluorochemical composition.Generally, the method of making the fluorinated polyether according toformula (I) will result in a mixture of fluorinated polyethers that havedifferent molecular weights and such a mixture can be used as such toprepare the fluorochemical component of the fluorochemical composition.In a preferred embodiment, such a mixture of fluorinated polyethercompounds according to formula (I) is free of fluorinated polyethercompounds having a perfluorinated polyether moiety having a molecularweight of less than 750 g/mol or alternatively the mixture containsfluorinated polyether compounds having a perfluorinated polyether moietyhaving a molecular weight of less than 750 g/mol in an amount of notmore than 10% by weight relative to total weight of fluorinatedpolyether compounds, preferably not more than 5% by weight and mostpreferably not more than 1% by weight.

The isocyanate component for making the fluorinated compound of thefluorochemical composition is selected from a polyisocyanate having atleast 3 isocyanate groups or a mixture of polyisocyanate compounds thaton average has more than 2 isocyanate groups per molecule such as forexample a mixture of a diisocyanate compound and a polyisocyanatecompound having 3 or more isocyanate groups.

The polyisocyanate compound may be aliphatic or aromatic and isconveniently a non-fluorinated compound. Generally, the molecular weightof the polyisocyanate compound will be not more than 1500 g/mol.Examples include hexamethylenediisocyanate,2,2,4-trimethyl-1,6-hexamethylenediisocyanate, and1,2-ethylenediisocyanate, dicyclohexylmethane-4,4′-diisocyanate,aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate,cyclic trimer of hexamethylenediisocyanate and cyclic trimer ofisophorone diisocyanate (isocyanurates); aromatic polyisocyanate such as4,4′-methylenediphenylenediisocyanate,4,6-di-(trifluoromethyl)-1,3-benzene diisocyanate,2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylenediisocyanate, 4,4′-diisocyanatodiphenylether,3,3′-dichloro-4,4′-diisocyanatodiphenylmethane,4,5′-diphenyldiisocyanate, 4,4′-diisocyanatodibenzyl,3,3′-dimethoxy-4,4′-diisocyanatodiphenyl,3,3′-dimethyl-4,4′-diisocyanatodiphenyl,2,2′-dichloro-5,5′-dimethoxy-4,4′-diisocyanato diphenyl,1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate,4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and1,8-dinitro-2,7-naphthylene diisocyanate and aromatic triisocyanatessuch as polymethylenepolyphenylisocyanate. Still further isocyanatesthat can be used for preparing the fluorinated compound includealicyclic diisocyanates such as3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aromatictri-isocyanates such as polymethylenepolyphenylisocyanate (PAPI); cyclicdiisocyanates such as isophorone diisocyanate (IPDI). Also useful areisocyanates containing internal isocyanate-derived moieties such asbiuret-containing tri-isocyanates such as that available from Bayer asDESMODUR™ N-100, isocyanurate-containing tri-isocyanates such as thatavailable from Huls AG, Germany, as IPDI-1890, andazetedinedione-containing diisocyanates such as that available fromBayer as DESMODUR™ TT. Also, other di- or tri-isocyanates such as thoseavailable from Bayer as DESMODUR™ L and DESMODUR™ W,tri-(4-isocyanatophenyl)-methane (available from Bayer as DESMODUR™ R)and DDI 1410 (available from Henkel) are suitable.

The optional coreactant typically comprises water or a non-fluorinatedorganic compound having one or more zerewitinoff hydrogen atoms.Examples include non-fluorinated organic compounds that have at leastone or two functional groups that are capable of reacting with anisocyanate group. Such functional groups include hydroxy, amino andthiol groups. Examples of such organic compounds include aliphaticmonofunctional alcohols, e.g., mono-alkanols having at least 1,preferably at least 6 carbon atoms, aliphatic monofunctional amines, apolyoxyalkylenes having 2, 3 or 4 carbon atoms in the oxyalkylene groupsand having 1 or 2 groups having at least one zerewitinoff hydrogen atom,polyols including diols such as polyether diols, e.g.,polytetramethylene glycol, polyester diols, dimer diols, fatty acidester diols, polysiloxane diols and alkane diols such as ethylene glycoland polyamines.

Examples of monofunctional alcohols include methanol, ethanol, n-propylalcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butylalcohol, n-amyl alcohol, t-amyl alcohol, 2-ethylhexanol, glycidol and(iso)stearylalcohol.

Fatty ester diols are preferably diols that include an ester functionderived from a fatty acid, preferably a fatty acid having at least 5carbon atoms and more preferably at least 8 carbon atoms. Examples offatty ester diols include glycerol mono-oleate, glycerol mono-stearate,glycerol mono-ricinoleate, glycerol mono-tallow, long chain alkyldi-esters of pentaerythritol having at least 5 carbon atoms in the alkylgroup. Suitable fatty ester diols are commercially available under thebrand RILANIT® from Henkel and examples include RILANIT® GMS, RILANIT®GMRO and RILANIT® HE.

Polysiloxane diols include polydialkylsiloxane diols andpolyalkylarylsiloxane diols. The polymerization degree of thepolysiloxane diol is preferably between 10 and 50 and more preferablybetween 10 and 30. Polysiloxane diols particularly include those thatcorrespond to one of the following two formulas:

wherein R¹ and R² independently represent an alkylene having 1 to 4carbon atoms, R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ independently represent analkyl group having 1 to 4 carbon atoms or an aryl group, L^(a)represents a trivalent linking group and m represents a value of 10 to50. L is for example a linear or branched alkylene that may contain oneor more catenary hetero atoms such as oxygen or nitrogen.

Further suitable diols include polyester diols. Examples include linearpolyesters available under the brand UNIFLEX™ from Union Camp andpolyesters derived from dimer acids or dimer diols. Dimer acids anddimer diols are well-known and are obtained by dimerisation ofunsaturated acids or diols in particular of unsaturated long chainaliphatic acids or diols (e.g. at least 5 carbon atoms). Examples ofpolyesters obtainable from dimer acids and/or dimer diols are thoseavailable under the brand PRIPLAST from Uniqema, Gouda, Netherlands.

Dimer diols include those that are commercially available from Uniqemaunder the brand PRIPOL™ which are believed to have been obtained fromdimerisation of unsaturated diols in particular of unsaturated longchain aliphatic diols (e.g., at least 5 carbon atoms).

According to a particularly preferred embodiment, the organic compoundwill include one or more water solubilising groups or groups capable offorming water solubilising groups so as to obtain a fluorinated compoundthat can more easily be dispersed in water. Additionally, by includingwater solubilising groups in the fluorinated compound, beneficial stainrelease properties may be obtained on the fibrous substrate. Suitablewater solubilising groups include cationic, anionic and zwitter ionicgroups as well as non-ionic water solubilising groups. Examples of ionicwater solubilising groups include ammonium groups, phosphonium groups,sulfonium groups, carboxylates, sulfonates, phosphates, phosphonates orphosphinates. Examples of groups capable of forming a water solubilisinggroup in water include groups that have the potential of beingprotonated in water such as amino groups, in particular tertiary aminogroups. Particularly preferred organic compounds are those organiccompounds that have only one or two functional groups capable ofreacting with NCO-group and that further include a non-ionicwater-solubilizing group. Typical non-ionic water solubilizing groupsinclude polyoxyalkylene groups. Preferred polyoxyalkylene groups includethose having 1 to 4 carbon atoms such as polyoxyethylene,polyoxypropylene, polyoxytetramethylene and copolymers thereof such aspolymers having both oxyethylene and oxypropylene units. Thepolyoxyalkylene containing organic compound may include one or twofunctional groups such as hydroxy or amino groups. Examples ofpolyoxyalkylene containing compounds include alkyl ethers of polyglycolssuch as e.g. methyl or ethyl ether of polyethyleneglycol, hydroxyterminated methyl or ethyl ether of a random or block copolymer ofethyleneoxide and propyleneoxide, amino terminated methyl or ethyl etherof polyethyleneoxide, polyethylene glycol, polypropylene glycol, ahydroxy terminated copolymer (including a block copolymer) ofethyleneoxide and propylene oxide, a diamino terminated poly(alkyleneoxide) such as JEFFAMINE™ ED, JEFFAMINE™ EDR-148 and poly(oxyalkylene)thiols.

Still further, the optional co-reactant may include an isocyanateblocking agent. The isocyanate blocking agent can be used alone or incombination with one or more other co-reactants described above.Isocyanate blocking agents are compounds that upon reaction with anisocyanate group yield a group that is unreactive at room temperaturewith compounds that at room temperature normally react with anisocyanate but which group at elevated temperature reacts withisocyanate reactive compounds. Generally, at elevated temperature theblocking group will be released from the blocked (poly)isocyanatecompound thereby generating the isocyanate group again which can thenreact with an isocyanate reactive group. Blocking agents and theirmechanisms have been described in detail in “Blocked isocyanates III.:Part. A, Mechanisms and chemistry” by Douglas Wicks and Zeno W. WicksJr., Progress in Organic Coatings, 36 (1999), pp. 14-172.

Preferred blocking agents include arylalcohols such as phenols, lactamssuch as ε-caprolactam, δ-valerolactam, γ-butyrolactam, oximes such asformaldoxime, acetaldoxime, cyclohexanone oxime, acetophenone oxime,benzophenone oxime, 2-butanone oxime or diethyl glyoxime. Furthersuitable blocking agents include bisulfite and triazoles.

In accordance with a particular embodiment, a perfluoroaliphatic groupmay be included in the fluorinated compound and the co-reactant may thencomprise a perfluoroaliphatic compound having one or more isocyanatereactive groups. By “perfluoroaliphatic groups” is meant groups thatconsist of carbon and fluorine without however including perfluorinatedend groups of the perfluorinated moiety. The perfluoroaliphatic groupcontains 3 to 18 carbon atoms but preferably has 3 to 6 carbon atoms, inparticular a C₄F₉— group. By including perfluoroaliphatic groups, inparticular C₄F₉— groups in the fluorinated polyether compound, one canimprove the solubility and/or dispersibility of the fluorinatedpolyether compound in the fluorochemical composition. Preferredfluorinated co-reactants will correspond to the formula:(R_(f) ⁴)_(x)-L-Y  (IV)wherein R_(f) ⁴ represents a perfluoroaliphatic group having 3 to 5 or 6carbon atoms, L represents a non-fluorinated organic divalent ormulti-valent linking group such as for example organic groups thatcomprise alkylene, carboxy, sulfonamido, carbonamido, oxy, alkyleneoxy,thio, alkylenethio and/or arylene. Y represents a functional grouphaving a Zerewitinoff hydrogen such as for example hydroxy, amino orthiol and x is an integer of 1 to 20, for example between 2 and 10.According to a particular embodiment, R_(f) ⁴ is C₄F₉— and x is 1.

Compounds according to formula (IV) in which x is 2 or more can beconveniently prepared through the polymerization of a perfluoroaliphaticcompound having a polymerizable group in the presence of afunctionalized chain transfer agent. Examples of such polymerizableperfluoroaliphatic compounds include those according to the formula:R_(f) ⁴-Q³-C(R^(e))═CH₂  (V)wherein R_(f) ⁴ is a perfluoroaliphatic group of 3 to 5 or 6 carbonatoms, preferably C₄F₉—, R^(e) is hydrogen or a lower alkyl of 1 to 4carbon atoms and Q³ represents a non-fluorinated organic divalentlinking group. The linking group Q³ links the perfluoroaliphatic groupto the free radical polymerizable group. Linking group Q³ is generallynon-fluorinated and preferably contains from 1 to about 20 carbon atoms.Q³ can optionally contain oxygen, nitrogen, or sulfur-containing groupsor a combination thereof, and Q³ is free of functional groups thatsubstantially interfere with free-radical polymerization (e.g.,polymerizable olefinic double bonds, thiols, and other suchfunctionality known to those skilled in the art). Examples of suitablelinking groups Q³ include straight chain, branched chain or cyclicalkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido,carbonamido, carbonyloxy, urethanylene, ureylene, and combinationsthereof such as sulfonamidoalkylene.

Specific examples of fluorinated aliphatic group containing monomersinclude:

CF₃CF₂CF₂CF₂CH₂CH₂OCOCR^(d)═CH₂;

CF₃(CF₂)₃CH₂OCOCR^(d)═CH₂;

CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂OCOCR^(d)═CH₂;

CF₃(CF₂)₃SO₂N(C₂H₅)CH₂CH₂OCOCR^(d)═CH₂;

CF₃(CF₂)₃SO₂N(CH₃)CH₂CH(CH₃)OCOCR^(d)═CH₂;

(CF₃)₂CFCF₂SO₂N(CH₃)CH₂CH₂OCOCR^(d)═CH₂; and

C₆F₁₃C₂H₄OOC—CR^(d)═CH₂

wherein R^(d) is hydrogen or methyl.

Examples of suitable chain transfer agents include compounds that havethe general formula:HS—R^(h)-A  (VI)wherein R^(h) represents a non-fluorinated organic divalent linkinggroup or a chemical bond and A represents a functional group that has aZerewitinoff hydrogen atom, Examples of functional groups A includeamino groups, hydroxy and acid groups. Specific examples of functionalchain transfer agents include 2-mercaptoethanol, mercaptoacetic acid,2-mercaptobenzoic acid, 3-mercapto-2-butanol, 2-mercaptosulfonic acid,2-mercaptoethylsulfide, 2-mercaptonicotinic acid, 4-hydroxythiophenol,3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 2-mercaptopropionicacid, N-(2-mercaptopropionyl)glycine, 2-mercaptopyridinol,mercaptosuccinic acid, 2,3-dimercaptopropanesulfonic acid,2,3-dimercaptopropanol, 2,3-dimercaptosuccinic acid,2,5-dimercapto-1,3,4-thiadiazole, 3,4-toluenedithiol, o-, m-, andp-thiocresol, 2-mercaptoethylamine, ethylcyclohexanedithiol,p-menthane-2,9-dithiol and 1,2-ethanedithiol. Preferred functionalizedend-capping agents include 2-mercaptoethanol,3-mercapto-1,2-propanediol, 4-mercaptobutanol, 11-mercaptoundecanol,mercaptoacetic acid, 3-mercaptopropionic acid, 12-mercaptododecanoicacid, 2-mercaptoethylamine, 1-chloro-6-mercapto-4-oxahexan-2-ol,2,3-dimercaptosuccinic acid, 2,3-dimercaptopropanol,3-mercaptopropyltrimethoxysilane, 2-chloroethanethiol,2-amino-3-mercaptopropionic acid, and compounds such as the adduct of2-mercaptoethylamine and caprolactam.

Specific examples of perfluoroaliphatic coreactants include:

C₄F₉—SO₂NR—CH₂CH₂OH;

C₄F₉—SO₂NR—CH₂CH₂—O—[CH₂CH₂O]_(t)OH wherein t is 1 to 5;

C₄F₉SO₂NRCH₂CH₂CH₂NH₂;

C₄F₉—SO₂NR—CH₂CH₂SH;

C₄F₉—SO₂N—(CH₂CH₂OH)₂; and

C₄F₉—SO₂NR—CH₂CH₂O(CH₂)_(s)OH wherein s is 2, 3, 4, 6, 8, 10 or 11

wherein R is hydrogen or a lower alkyl of 1 to 4 carbons such as methyl,ethyl and propyl.

The condensation reaction to prepare the fluorinated compound of thefluorochemical composition can be carried out under conventionalconditions well-known to those skilled in the art. Preferably thereaction is run in the presence of a catalyst and typically, thereaction will be carried out such that all isocyanate groups have beenreacted and the obtained reaction product is free of isocyanate groups.Suitable catalysts include tin salts such as dibutyltin dilaurate,stannous octanoate, stannous oleate, tin dibutyldi-(2-ethyl hexanoate),stannous chloride; and others known to those skilled in the art. Theamount of catalyst present will depend on the particular reaction, andthus it is not practical to recite particular preferred concentrations.Generally, however, suitable catalyst concentrations are from about0.001 percent to about 10 percent, preferably about 0.1 percent to about5 percent, by weight based on the total weight of the reactants.

The condensation reaction is preferably carried out under dry conditionsin a common organic solvent that does not contain Zerewitinoff hydrogenssuch as ethyl acetate, acetone, methyl isobutyl ketone, toluene andfluorinated solvents such hydrofluoroethers and trifluorotoluene.Suitable reaction temperatures will be easily determined by thoseskilled in the art based on the particular reagents, solvents, andcatalysts being used. While it is not practical to enumerate particulartemperatures suitable for all situations, generally suitabletemperatures are between about room temperature and about 120° C.

Generally the reaction is carried out such that between 1 and 100% ofthe isocyanate groups of the polyisocyanate compound or mixture ofpolyisocyanate compounds is reacted with the perfluorinated polyethercompound according to formula (I). Preferably between 5 and 60% and morepreferably 10% to 50% of the isocyanate groups is reacted with theperfluorinated polyether compound and the remainder is reacted with oneor more co-reactants as described above. An especially preferredfluorinated compound is obtained by reacting 10 to 30% of the isocyanategroups with the perfluorinated polyether compound according to formula(I), between 90 and 30% of the isocyanate groups with an isocyanateblocking agent and between 0 and 40% of the isocyanate groups with wateror a non-fluorinated organic compound other than an isocyanate blockingagent.

The fluorinated compound of the fluorochemical composition typicallywill have a molecular weight such that it is readily dissolved ordispersed in water or an organic solvent. Generally, the molecularweight of the fluorinated compound is not more than 100,000 g/mol,preferably not more than 50,000 g/mol with a typical range being between1500 g/mol and 15,000 g/mol or between 1500 g/mol and 5,000 g/mol. Whena mixture of fluorinated compounds is used, the aforementioned molecularweights represent weight average molecular weights.

The fluorochemical composition comprises a dispersion or solution of thefluorinated compound in water or an organic solvent. The term“dispersion” in connection with this invention includes dispersions of asolid in a liquid as well as liquid in liquid dispersions, which arealso called emulsions. Generally, the amount of fluorinated compoundcontained in the treating composition is between 0.01 and 4% by weight,preferably between 0.05 and 3% by weight based on the total weight ofthe fluorochemical composition. Higher amounts of fluorinated compoundof more than 4% by weight, for example up to 10% by weight may be usedas well, particularly if the uptake of the fluorochemical composition bythe substrate is low. Generally, the fluorochemical treating compositionwill be prepared by diluting a more concentrated fluorochemicalcomposition to the desired level of fluorinated compound in the treatingcomposition. The concentrated fluorochemical composition can contain thefluorinated compound in an amount of up to 70% by weight, typicallybetween 10% by weight and 50% by weight.

When the fluorochemical composition is in the form of a dispersion inwater or an organic solvent, the weight average particle size of thefluorinated compound particles is preferably not more than 400 nm, morepreferably is not more than 300 nm.

Most preferably, the fluorochemical composition is an aqueous dispersionof the fluorinated compound. Such dispersion may be non-ionic, anionic,cationic or zwitterionic. The dispersion is preferably stabilised usingnon-fluorinated surfactants, such as non-ionic polyoxyalkylene, inparticular polyoxyethylene surfactants, anionic non-fluorinatedsurfactants, cationic non-fluorinated surfactants and zwitterionicnon-fluorinated surfactants. Specific examples of non-fluorinatedsurfactants that can be used are nonionic types such as EMULSOGEN™ EPN207 (Clariant) and TWEEN™ 80 (ICI), anionic types such as lauryl sulfateand sodium dodecyl benzene sulfonate, cationic types such as ARQUAD™T-50 (Akzo), ETHOQUAD™ 18-25 (Akzo) or amphoteric types such as laurylamineoxide and cocamido propyl betaine. The non-fluorinated surfactantis preferably present in an amount of about 1 to about 25 parts byweight, preferably about 2 to about 10 parts by weight, based on 100parts by weight of the fluorochemical composition.

Alternatively, a solution or dispersion of the fluorinated compound inan organic solvent can be used as the fluorochemical treatingcomposition. Suitable organic solvents include alcohols such asisopropanol, methoxy propanol and t.butanol, ketones such as isobutylmethyl ketone and methyl ethylketone, ethers such as isoptopylether,esters such ethylacetate, butylacetate or methoxypropanol acetate or(partially) fluorinated solvents such as HCFC-141b, HFC-4310mee andhydrofluoroethers such as HFE-7100 or HEM-7200 available from 3MCompany.

The fluorochemical composition may contain further additives such asbuffering agent, agents to impart fire proofing or antistaticproperties, fungicidal agents, optical bleaching agents, sequesteringagents, mineral salts and swelling agents to promote penetration. In aparticular embodiment, the fluorochemical composition may containadditionally a non-fluorinated organic compound, wherein thenon-fluorinated organic compound is capable of improving relative to thefluorochemical composition without the non-fluorinated organic compound,the oil repellency or water repellency that can be achieved by thefluorochemical composition on a fibrous substrate or the durability ofone or both of the repellency properties. Such non-fluorinated organiccompounds are sometimes called extenders. Suitable extenders for use inthe fluorochemical composition include non-fluorinated organic compoundsthat have one or more blocked isocyanate groups, so called blockedisocyanate compounds, or a carbodiimide compound. Preferred blockedisocyanate extenders are blocked polyisocyanates that at a temperatureof less than 150° C. are capable of reacting with an isocyanate reactivegroup, preferably through deblocking of the blocking agent at elevatedtemperature. Preferred blocking agents include arylalcohols such asphenols, lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam,oximes such as formaldoxime, acetaldoxime, methyl ethyl ketone oxime,cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2-butanoneoxime or diethyl glyoxime. Further suitable blocking agents includebisulfite and triazoles.

According to a particular embodiment of the invention, the blockedpolyisocyanate may comprise the condensation product of apolyisocyanate, for example a di- or triisocyanate, a blocking agent anda non-fluorinated organic compound other than the blocking agent andhaving one or more isocyanate reactive groups such as a hydroxy, aminoor thiol group. Examples of such non-fluorinated organic compounds otherthan the blocking agent include those described above as optionalco-reactant in the preparation of the fluorinated compound.

The carbodiimide compound can be an aromatic or aliphatic carbodiimidecompound and may include a polycarbodiimide. Carbodiimides that can beused have been described in for example U.S. Pat. No. 4,668,726, U.S.Pat. No. 4,215,205, U.S. Pat. No. 4,024,178, U.S. Pat. No. 3,896,251, WO93/22282, U.S. Pat. No. 5,132,028, U.S. Pat. No. 5,817,249, U.S. Pat.No. 4,977,219, U.S. Pat. No. 4,587,301, U.S. Pat. No. 4,487,964, U.S.Pat. No. 3,755,242 and U.S. Pat. No. 3,450,562. Particularly suitablecarbodiimides for use in this invention include those corresponding tothe formula (VII):R¹—[N═C═N—R³]_(u)—N═C═N—R²  (VII)wherein u has a value of 1 to 20, typically 1 or 2, R¹ and R² eachindependently represent a hydrocarbon group, in particular a linear,branched or cyclic aliphatic group preferably having 6 to 18 carbonatoms and R³ represents a divalent linear, branched or cyclic aliphaticgroup.

The aliphatic carbodiimide extenders of formula VII can be synthesizedin a 1-step process by reacting aliphatic diisocyanates with analiphatic mono-isocyanate as a chain terminator at 130 to 170° C. in thepresence of a phospholine oxide or other suitable carbodiimide formationcatalyst. Preferably the reaction is carried out in the absence ofsolvents under inert atmosphere, but high-boiling non-reactive solventssuch as methyl isobutyl ketone can be added as diluents. The mole ratioof diisocyanate to mono-isocyanate can be varied from 0.5 to 10,preferably 1 to 5.

Examples of aliphatic diisocyanates for the preparation of thecarbodiimide compounds of formula (VII) include isophorone diisocyanate,dimer diacid diisocyanate, 4,4′ dicyclohexyl methane diisocyanate.Examples of mono-isocyanates are n.butyl isocyanate and octadecylisocyanate. Representative examples of suitable carbodiimide formationcatalysts are described in e.g.; U.S. Pat. No. 2,941,988, U.S. Pat. No.3,862,989 and U.S. Pat. No. 3,896,251. Examples include1-ethyl-3-phospholine, 1-ethyl-3-methyl-3-phospholine-1-oxide,3-methyl-1-phenyl-3-phospholine-1-oxide and bicyclic terpene alkyl orhydrocarbyl aryl phosphine oxide. The particular amount of catalyst useddepends on the reactivity of the catalyst and the isocyanates beingused. A concentration of 0.2 to 5 parts of catalyst per 100 g ofdiisocyanate is suitable.

In an alternative approach the aliphatic diisocyanates can be firstreacted with monofunctional alcohols, amines or thiols followed bycarbodiimide formation in a second step.

The fluorochemical composition may contain also further fluorochemicalcompounds other than the fluorinated compound comprising the reactionproduct as described above. For example, the fluorochemical compositionmay contain fluorochemical compounds that are based on or derived fromperfluoroaliphatic compounds. Nevertheless, it is not necessary toinclude such compounds in the fluorochemical composition. Also, ifperfluoroaliphatic based compounds are included in the composition, theyare preferably compounds based on short chain perfluoroaliphatics suchas compounds containing C₄F₉— groups.

In a preferred embodiment of the present invention, the fluorochemicalcomposition will be free of or substantially free of perfluorinatedpolyether moieties having a molecular weight of less than 750 g/moland/or perfluoroaliphatic groups of more than 5 or 6 carbons. By theterm “perfluoroaliphatic groups” is meant groups consisting of carbonand fluorine without including perfluorinated end groups of theperfluorinated polyether moieties. By the term “substantially free of”is meant that the particular perfluorinated polyether moieties arepresent in amounts of not more than 10% by weight, preferably not morethan 5% by weight and most preferably not more than 1% by weight basedon the total weight of perfluorinated polyether moieties in thecomposition and that the particular perfluoroaliphatic groups havingmore than 5 or 6 carbons are present in amounts of not more than 10% byweight, preferably not more than 5% by weight and most preferably notmore than 1% by weight based on the total weight of perfluoroaliphaticgroups in the composition. Compositions that are free of orsubstantially free of these moieties or groups are preferred because oftheir beneficial environmental properties.

In order to affect treatment of the fibrous substrate the fibroussubstrate is contacted with the fluorochemical composition of theinvention. For example, the substrate can be immersed in thefluorochemical treating composition. The treated substrate can then berun through a padder/roller to remove excess fluorochemical compositionand dried. The treated substrate may be dried at room temperature byleaving it in air or may alternatively or additionally be subjected to aheat treatment, for example, in an oven. This heat treatment istypically carried out at temperatures between about 50° C. and about190° C. depending on the particular system or application method used.In general, a temperature of about 120° C. to 170° C., in particular ofabout 150° C. to about 170° C. for a period of about 20 seconds to 10minutes, preferably 3 to 5 minutes, is suitable. Alternatively, thechemical composition can be applied by spraying the composition on thefibrous substrate.

It was found that with fluorochemical compositions of this invention,good to excellent oil, water repellent properties and/or stain releaseproperties on the fibrous substrate can be achieved. Moreover, theseproperties can be achieved without subjecting the fibrous substrate to aheat treatment (i.e., the properties can be achieved upon air drying thefibrous substrate after the application of the composition). Also, itwas observed that the repellency properties are durable, i.e., evenafter several washing or dry cleaning cycles, the repellency propertiescan be substantially maintained. The compositions furthermore in manyinstances do not negatively affect the soft feel of the fibroussubstrates or may even improve the soft feel of the fibrous substrate.

The amount of the treating composition applied to the fibrous substrateis chosen so that a sufficiently high level of the desired propertiesare imparted to the substrate surface preferably without substantiallyaffecting the look and feel of the treated substrate. Such amount isusually such that the resulting amount of the fluoropolymer on thetreated fibrous substrate will be between 0.05% and 3% by weight,preferably between 0.2 and 1% by weight based on the weight of thefibrous substrate. The amount which is sufficient to impart desiredproperties can be determined empirically and can be increased asnecessary or desired. According to a particularly preferred embodiment,the treatment is carried out with a composition and under conditionssuch that the total amount of perfluorinated polyether groups having amolecular weight of less than 750 g/mol and/or perfluoroaliphatic groupsof more than 6 carbon atoms is not more than 0.1%, preferably not morethan 0.05% by weight based on the weight of the fibrous substrate.

Fibrous substrates that can be treated with the fluorochemicalcomposition include in particular textile and carpet. The fibroussubstrate may be based on synthetic fibers, e.g., polyester, polyamideand polyacrylate fibers or natural fibers, e.g., cellulose fibers aswell as mixtures thereof. The fibrous substrate may be a woven as wellas a non-woven substrate.

The stain-release properties may be enhanced by the addition of astain-release composition. The term “stain release” used herein refersto the property of ready release of stains that have been absorbed byfibrous materials or leather. The ratio of the stain release compound(s)to the repellent compound(s) may comprise from about 10:90 to 90:10weight percent. The individual components (A) and (B) can be prepared assolvent solution, blended and then emulsified, or separately preparedemulsions may be blended. The separately prepared solvent solutions oremulsions maybe concentrated solutions of emulsions, that may besubsequently diluted to preferred concentrations prior to use.

The stain release composition is advantageously a fluorochemicalurethane stain release composition such as is described in U.S. Pat. No.6,646,088 (Fan et al.), incorporated herein by reference. These compriseone or more urethane oligomers of at least two repeating units selectedfrom the group consisting of fluorine-containing urethane oligomers andlong-chain hydrocarbon-containing urethane oligomers. These urethaneoligomers comprise the reaction product of (a) one or morepolyfunctional isocyanate compounds; (b) one or more polyols; (c) one ormore monoalcohols selected from the group consisting of fluorochemicalmonoalcohols, optionally substituted long-chain hydrocarbonmonoalcohols, and mixtures thereof; (d) one or more silanes; andoptionally (e) one or more water-solubilizing compounds comprising oneor more water-solubilizing groups and at least one isocyanate-reactivehydrogen containing group.

Preferred classes of urethane oligomers that may be present arerepresented by the following formulas (III) through (VI):R_(f)¹⁰ZR¹²—O(—CONH-Q(A)_(m)-NHCO—O¹³O—)_(n)CONH-Q(A)-NHCO—X′¹¹Si(Y)₃  (III)R_(f) ¹⁰ZR¹²—O(—CONH-Q(A)_(m)-NHCO—OR¹³O—)_(n)CONHR¹¹Si(Y)₃  (IV)R¹⁴—O(—CONH-Q(A)_(m)-NHCO—OR¹³O—)_(n)CONH-Q(A)-NHCO—X′R¹¹Si(Y)₃  (V)R¹⁴—O(—CONH-Q(A)_(m)-NHCO—OR¹³O—)_(n)CONHR¹¹Si(Y)₃  (VI)wherein:

R_(f) ¹⁰ZR¹²— is a residue of at least one of the fluorochemicalmonoalcohols;

R_(f) ¹⁰ is a perfluoroalkyl group having 3 to about 8 carbon atoms, ora perfluoroheteroalkyl group having 3 to about 50 carbon atoms;

Z is a covalent bond, sulfonamido (—SO₂NR—), or carboxamido (—CONR—)where R is hydrogen or alkyl;

R¹¹ is an alkylene, heteroalkylene, aralkylene, or heteroaralkylenegroup;

R¹² is a divalent straight- or branched-chain alkylene, cycloalkylene,or heteroalkylene group of 1 to 14 carbon atoms, preferably 1 to 8carbon atoms, more preferably 1 to 4 carbon atoms, and most preferablytwo carbon atoms, and preferably R² is alkylene or heteroalkylene of 1to 14 carbon atoms;

Q is a multi-valent organic group which is a residue of thepolyfunctional isocyanate compound;

R¹³ is a divalent organic group which is a residue of the polyol and maybe substituted with or contain (i) water-solubilizing groups selectedfrom the group consisting of carboxylate, sulfate, sulfonate,phosphonate, ammonium, quaternary ammonium, and mixtures thereof and(ii) perfluorinated groups;

X′ is —O—, —S—, or —N(R)—, wherein R is hydrogen or alkyl;

R¹⁴ is an optionally substituted long-chain hydrocarbon derived from thelong-chain hydrocarbon monoalcohol;

each Y is independently a hydroxy; a hydrolyzable moiety selected fromthe group consisting of alkoxy, acyloxy, heteroalkoxy, heteroacyloxy,halo, and oxime; or a non-hydrolyzable moiety selected from the groupconsisting of phenyl, alicyclic, straight-chain aliphatic, andbranched-chain aliphatic, wherein at least one Y is a hydrolyzablemoiety.

A is selected from the group consisting of R_(f) ¹⁰ZR¹²—OCONH—,(Y)₃SiR¹¹XCONH—, (Y)₃SiR¹¹NHCOOR¹³OCONH—, and W—CONH—, wherein W is aresidue of the water-solubilizing compound comprising one or morewater-solubilizing groups;

m is an integer from 0 to 2; and

n, which is the number of repeating units, is an integer from 2 to 10.

The polisocyanate component of the stain release composition may beselected from those previously described. Preferred polyisocyanates, ingeneral, include those selected from the group consisting ofhexamethylene 1,6-diisocyanate (HDI), 1,12-dodecane diisocyanateisophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane4,4′-diisocyanate, MDI, derivatives of all the aforementioned, includingDESMODUR™ N-100, N-3200, N-3300, N-3400, N-3600, and mixtures thereof.

Polyols suitable for use in preparing the chemical compositions of thepresent invention include those organic polyols that have an averagehydroxyl functionality of at least about 2 (preferably, about 2 to 5;more preferably, about 2 to 3; most preferably, about 2, as diols aremost preferred). The hydroxyl groups can be primary or secondary, withprimary hydroxyl groups being preferred for their greater reactivity.Mixtures of diols with polyols that have an average hydroxylfunctionality of about 2.5 to 5 (preferably about 3 to 4; morepreferably, about 3) can also be used. It is preferred that suchmixtures contain no more than about 20 percent by weight of suchpolyols, more preferably no more than about 10 percent, and mostpreferably no more than about 5 percent. Preferred mixtures are mixturesof diols and triols.

Suitable polyols include those that comprise at least one aliphatic,heteroaliphatic, alicyclic, heteroalicyclic, aromatic, heteroaromatic,or polymeric moiety. Preferred polyols are aliphatic or polymericpolyols that contain hydroxyl groups as terminal groups or as groupsthat are pendant from the backbone chain of the polyol.

The molecular weight (that is, the number average molecular weight) ofhydrocarbon polyols can generally vary from about 60 to about 2000,preferably, from about 60 to about 1000, more preferably, from about 60to about 500, most preferably, from about 60 to about 300. Theequivalent weight (that is, the number average equivalent weight) ofhydrocarbon polyols generally can be in the range of about 30 to about1000, preferably, from about 30 to about 500, more preferably, fromabout 30 to about 250. Polyols of higher equivalent weight can have atendency to reduce the stain-release properties provided by the chemicalcompositions of the present invention unless the polyol contains anR_(f) group or the polyol comprises a perfluoropolyether. If the polyolcomprises a perfluoropolyether, it can have a molecular weight as highas approximately 7000 and can still provide adequate stain-releaseproperties.

When the polyols of the present invention are diols, the diols can besubstituted with or contain other groups. Thus, a preferred diol isselected from the group consisting of a branched- or straight-chainhydrocarbon diol, a diol containing at least one solubilizing group, afluorinated diol comprising a monovalent or divalent perfluorinatedgroup, a diol comprising a silane group, a polyalkylsiloxane diol, apolyarylsiloxane diol, and mixtures thereof. Solubilizing groups includecarboxylate, sulfate, sulfonate, phosphate, phosphonate, ammonium,quaternary ammonium, and the like.

Perfluorinated monovalent groups (R_(f)) may be perfluoroalkyl andperfluoroheteroalkyl, and perfluorinated divalent groups may beperfluoroalkylene and perfluoroheteroalkylene. Perfluoroalkyl groups arepreferred, with perfluoroalkyl groups having from 2 to 6 carbon atomsbeing more preferred and perfluoroalkyl groups having 4 carbon atomsbeing most preferred. Another embodiment comprises perfluoroheteroalkylgroups having 6 to 50 carbon atoms. Perfluorinated divalent groups arepreferably perfluoroheteroalkylene groups. Perfluoroheteroalkylenegroups are preferably perfluoropolyether groups having from about 3 toabout 50 carbon atoms.

The silane groups of the diol may contain one, two, or threehydrolyzable groups on the silicon atom. Hydrolyzable groups are asdefined below. Polyalkylsiloxane diols include, but are not limited to,hydroxyalkyl terminated polydimethyl siloxanes,polymethyloctadecylsiloxane, polydimethylmethyloctadecylsiloxane,polydimethyldodecyltetradecylsiloxane, polymethylhexadecylsiloxane,polymethyloctylsiloxane, polymethyl-3,3,3-trifluoropropylsiloxane, andthe like. Polyarylsiloxane diols are essentially the same as thepolyalkylsiloxanes with some or all of the methyl groups replaced withphenyl groups, such as hydroxyalkyl terminated polydiphenylsiloxane andhydroxyalkyl terminated dimethyl-diphenylsiloxane copolymer.

Representative examples of suitable non-polymeric polyols includealkylene glycols, polyhydroxyalkanes, and other polyhydroxy compounds.The alkylene glycols include, for example, 1,2-ethanediol;1,2-propanediol; 3-chloro-1,2-propanediol; 1,3-propanediol;1,3-butanediol; 1,4-butanediol; 2-methyl-1,3-propanediol;2,2-dimethyl-1,3-propanediol (neopentylglycol); 2-ethyl-1,3-propanediol;2,2-diethyl-1,3-propanediol; 1,5-pentanediol; 2-ethyl-1,3-pentanediol;2,2,4-trimethyl-1,3-pentanediol; 3-methyl-1,5-pentanediol; 1,2-, 1,5-,and 1,6-hexanediol; 2-ethyl-1,6-hexanediol;bis(hydroxymethyl)cyclohexane; 1,8-octanediol; bicyclo-octanediol;1,10-decanediol; tricyclo-decanediol; norbornanediol; and1,18-dihydroxyoctadecane.

The polyhydroxyalkanes include, for example, glycerine;trimethylolethane; trimethylolpropane;2-ethyl-2-(hydroxymethyl)-1,3-propanediol; 1,2,6-hexanetriol;pentaerythritol; quinitol; mannitol; and sorbitol.

The other polyhydroxy compounds include, for example, such asdi(ethylene glycol); tri(ethylene glycol); tetra(ethylene glycol);tetramethylene glycol; dipropylene glycol; diisopropylene glycol;tripropylene glycol; bis(hydroxymethyl)propionic acid;N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane; bicine;N-bis(2-hydroxyethyl) perfluorobutylsulfonamide;1,11-(3,6-dioxaundecane)diol; 1,14-(3,6,9,12-tetraoxatetradecane)diol;1,8-(3,6-dioxa-2,5,8-trimethyloctane)diol;1,14-(5,10-dioxatetradecane)diol; castor oil; 2-butyne-1,4-diol;N,N-bis(hydroxyethyl)benzamide; 4,4′-bis(hydroxymethyl)diphenylsulfone;1,4-benzenedimethanol; 1,3-bis(2-hydroxyethyoxy)benzene;1,2-dihydroxybenzene; resorcinol; 1,4-dihydroxybenzene; 3,5-, 2,6-,2,5-, and 2,4-dihydroxybenzoic acid; 1,6-, 2,6-, 2,5-, and2,7-dihydroxynaphthalene; 2,2′- and 4,4′-biphenol;1,8-dihydroxybiphenyl; 2,4-dihydroxy-6-methyl-pyrimidine;4,6-dihydroxypyrimidine; 3,6-dihydroxypyridazine; bisphenol A;4,4′-ethylidenebisphenol; 4,4′-isopropylidenebis(2,6-dimethylphenol);bis(4-hydroxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)-1-phenylethane(bisphenol C); 1,4-bis(2-hydroxyethyl)piperazine; bis(4-hydroxyphenyl)ether;1,4-bis(1-hydroxy-1,1-dihydroperfluoroethoxyethoxy)perfluoro-n-butane(HOCH₂CF₂OC₂F₄O(CF₂)₄OC₂F₄OCF₂CH₂OH);1,4-bis(1-hydroxy-1,1-dihydroperfluoropropoxy)perfluoro-n-butane(HOCH₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH); as well as other aliphatic,heteroaliphatic, saturated alicyclic, aromatic, saturatedheteroalicyclic, and heteroaromatic polyols; and the like, and mixturesthereof.

Representative examples of useful polymeric polyols includepolyoxyethylene, polyoxypropylene, and ethylene oxide-terminatedpolypropylene glycols and triols of molecular weights from about 200 toabout 2000, corresponding to equivalent weights of about 100 to about1000 for the diols or about 70 to about 700 for triols;polytetramethylene glycols of varying molecular weight;polydialkylsiloxane diols of varying molecular weight;hydroxy-terminated polyesters and hydroxy-terminated polylactones (e.g.,polycaprolactone polyols); hydroxy-terminated polyalkadienes (e.g.,hydroxyl-terminated polybutadienes); and the like. Mixtures of polymericpolyols can be used if desired.

Useful commercially available polymeric polyols include CARBOWAX™poly(ethylene glycol) materials in the number average molecular weight(M_(n)) range of from about 200 to about 2000 (available from UnionCarbide Corp., Danbury, Conn.); poly(propylene glycol) materials such asPPG-425 (available from Lyondell Chemical Company, Houston, Tex.); blockcopolymers of poly(ethylene glycol) and polypropylene glycol) such asPLURONIC™ L31 (available from BASF Corporation, Mount Olive, N.J.);fluorinated oxetane polyols made by the ring-opening polymerization offluorinated oxetane such as POLY-3-FOX™ (available from OmnovaSolutions, Inc., Akron Ohio); polyetheralcohols prepared by ring openingaddition polymerization of a fluorinated organic group substitutedepoxide with a compound containing at least two hydroxyl groups asdescribed in U.S. Pat. No. 4,508,916 (Newell et al); perfluoropolyetherdiols such as FOMBLIN™ ZDOL (HOCH₂CF₂O(CF₂O)₈₋₁₂(CF₂CF₂O)₈₋₁₂CF₂CH₂OH,available from Ausimont, Inc., Thorofare, N.J.); Bisphenol A ethoxylate,Bisphenol A propyloxylate, and Bisphenol A propoxylate/ethoxylate(available from Sigma-Aldrich, Milwaukee, Wis.); polytetramethyleneether glycols such as POLYMEG™ 650 and 1000 (available from Quaker OatsCompany, Chicago, Ill.) and the TERATHANE™ polyols (available from E.I.duPont de Nemours, filmgton, Del.); hydroxyl-terminated polybutadieneresins such as the POLY BD™ materials (available from Elf Atochem,Philadelphia, Pa.); the “PeP” series (available from Wyandotte ChemicalsCorporation, Wyandotte, Mich.) of polyoxyalkylene tetrols havingsecondary hydroxyl groups, for example, “PeP” 450, 550, and 650;polycaprolactone polyols with M_(n) in the range of about 200 to about2000 such as TONE™ 0201, 0210, 0301, and 0310 (available from UnionCarbide Corp., Danbury, Conn.); “PARAPLEX™ U-148” (available from Rohmand Haas Co., Philadelphia, Pa.), an aliphatic polyester diol; polyesterpolyols such as the MULTRON™ poly(ethyleneadipate)polyols (availablefrom Mobay Chemical Corp., Irvine, Calif.); polycarbonate diols such asDURACARB™ 120, a hexanediol carbonate with M_(n)=900 (available from PPGIndustries, Inc., Pittsburgh, Pa.); and the like; and mixtures thereof.

Preferred polyols include 2,2-bis(hydroxymethyl)propionic acid;N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane; bicine;3,5-dihydroxybenzoic acid; 2,4-dihydroxybenzoic acid;N-bis(2-hydroxyethyl)perfluorobutylsulfonamide; 1,2-ethanediol; 1,2- and1,3-propanediol; 1,3- and 1,4-butanediol; neopentylglycol;1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,2-, 1,5-, and1,6-hexanediol; bis(hydroxymethyl)cyclohexane; 1,8-octanediol;1,10-decanediol; di(ethylene glycol); tri(ethylene glycol);tetra(ethylene glycol); di(propylene glycol); di(isopropylene glycol);tri(propylene glycol); poly(ethylene glycol) diols (number averagemolecular weight of about 200 to about 1500); poly(di(ethylene glycol)phthalate) diol (having number average molecular weights of, forexample, about 350 or about 575); poly(propylene glycols) diols (numberaverage molecular weight of about 200 to about 500); block copolymers ofpoly(ethylene glycol) and poly(propylene glycol) such as PLURONIC™ L31(available from BASF Corporation, Mount Olive, N.J.);polydimethylsiloxane diol; fluorinated oxetane polyols made by thering-opening polymerization of fluorinated oxetane such as POLY-3-FOX™(available from Omnova Solutions, Inc., Akron Ohio); polyetheralcoholsprepared by ring opening addition polymerization of a fluorinatedorganic group substituted epoxide with a compound containing at leasttwo hydroxyl groups as described in U.S. Pat. No. 4,508,916 (Newell etal); perfluoropolyether diols such as FOMBLIN™ ZDOL(HOCH₂CF₂O(CF₂O)₈₋₁₂(CF₂CF₂)₈₋₁₂CF₂CH₂OH, available from Ausimont, Inc.,Thorofare, N.J.);1,4-bis(1-hydroxy-1,1-dihydroperfluoroethoxyethoxy)perfluoro-n-butane(HOCH₂CF₂OC₂F₄O(CF₂)₄OC₂F₄OCF₂CH₂OH);1,4-bis(1-hydroxy-1,1-dihydroperfluoropropoxy)perfluoro-n-butane(HOCH₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH); polycaprolactone diols (number averagemolecular weight of about 200 to about 600); resorcinol; hydroquinone;1,6-, 2,5-, 2,6-, and 2,7-dihydroxynaphthalene; 4,4′-biphenol; bisphenolA; bis(4-hydroxyphenyl)methane; and the like; and mixtures thereof.

More preferred polyols include bis(hydroxymethyl)propionic acid; bicine;N-bis(2-hydroxyethyl)perfluorobutylsulfonamide; 1,2-ethanediol; 1,2- and1,3-propanediol; 1,4-butanediol; neopentylglycol; 1,2- and1,6-hexanediol; di(ethylene glycol); tri(ethylene glycol);1,4-bis(1-hydroxy-1,1-dihydroperfluoropropoxy)perfluoro-n-butane(HOCH₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH); fluorinated oxetane polyols made bythe ring-opening polymerization of fluorinated oxetane such asPOLY-3-FOX™ (available from Omnova Solutions, Inc., Akron Ohio);poly(di(ethylene glycol) phthalate) diol (having number averagemolecular weights of, for example, about 350 or about 575);poly(ethylene glycol) diols (having number average molecular weights of,for example, about 200, 300, 400); polydimethylsiloxane diol;polypropylene glycol (having a number average molecular weight of, forexample, about 425); dimer diol; polycaprolactone diol (having a numberaverage molecular weight of, for example, about 530);3,5-dihydroxybenzene; bisphenol A; resorcinol; hydroquinone; andmixtures thereof.

Fluorochemical monoalcohols suitable for use in preparing the chemicalcompositions of the present invention include those that comprise atleast one R_(f) ¹⁰ group. The R_(f) ¹⁰ groups can containstraight-chain, branched-chain, or cyclic fluorinated alkylene groups orany combination thereof. The R_(f) ¹⁰ groups can optionally contain oneor more heteroatoms (i.e. oxygen, sulfur, and/or nitrogen) in thecarbon-carbon chain so as to form a carbon-heteroatom-carbon chain (i.e.a heteroalkylene group). Fully-fluorinated groups are generallypreferred, but hydrogen or chlorine atoms can also be present assubstituents, provided that no more than one atom of either is presentfor every two carbon atoms. It is additionally preferred that any R_(f)¹⁰ group contain at least about 40% fluorine by weight, more preferablyat least about 50% fluorine by weight. The terminal portion of the groupis generally fully-fluorinated, preferably containing at least threefluorine atoms, e.g., CF₃O—, CF₃CF₂—, CF₃CF₂CF₂—, (CF₃)₂N—, (CF₃)₂CF—,SF₅CF₂—. Perfluorinated aliphatic groups (i.e., those of the formulaC_(n)F_(2n+1)—) wherein n is 2 to 6 inclusive are the preferred R_(f)groups, with n=3 to 5 being more preferred and with n=4 being the mostpreferred.

Useful fluorine-containing monoalcohols include compounds of thefollowing formula II:R_(f) ¹⁰-Z-R¹²—OH  formula (II)wherein:

-   -   R_(f) ¹⁰ is a perfluoroalkyl group or a perfluoroheteroalkyl        group as defined above;    -   Z is a connecting group selected from a covalent bond, a        sulfonamido group, a carboxamido group, a carboxyl group, or a        sulfinyl group; and    -   R¹² is a divalent straight- or branched-chain alkylene,        cycloalkylene, or heteroalkylene group of 1 to 14 carbon atoms,        preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon        atoms, and most preferably two carbon atoms.    -   Representative examples of useful fluorine-containing        monoalcohols include the following:        -   CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₃SO₂N(CH₃)CH(CH₃)CH₂OH,        -   CF₃(CF₂)₃SO₂N(CH₃)CH₂CH(CH₃)OH,        -   CF₃(CF₂)₃SO₂N(CH₂CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂SCH₂CH₂OH,        -   C₆F₁₃SO₂N(CH₃)(CH₂)₄OH,        -   CF₃(CF₂)₇SO₂N(H)(CH₂)₃OH,        -   C₈F₁₇SO₂N(CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₇SO₂N(CH₃)(CH₂)₄OH,        -   C₈F₁₇SO₂N(CH₃)(CH₂)₁₁OH,        -   CF₃(CF₂)₇SO₂N(CH₂CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₆OH,        -   CF₃(CF₂)₇SO₂N(C₂H₅)(CH₂)₁₁OH,        -   CF₃(CF₂)₆SO₂N(C₃H₇)CH₂OCH₂CH₂CH₂OH,        -   CF₃ (CF₂)₇SO₂N(CH₂CH₂CH₃)CH₂CH₂OH,        -   CF₃ (CF₂)₉SO₂N(CH₂CH₂CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₇SO₂N(C₄H₉)CH₂CH₂OH,        -   CF₃(CF₂)₇SO₂N(C₄H₉)(CH₂)₄OH,        -   2-(N-methyl-2-(4-perfluoro-(2,6-diethylmorpholinyl))perfluoroethylsulfonamido)ethanol,        -   C₃F₇CONHCH₂CH₂OH,        -   C₇F₁₅CON(CH₃)CH₂CH₂OH,        -   C₇F₁₅CON(C₂H₅)CH₂CH₂OH,        -   C₈F₁₇CON(C₂H₅)CH₂CH₂OH,        -   C₈F₁₇CON(CH₃)(CH₂)₁₁OH,        -   C₄F₉CF(CF₃)CON(H)CH₂CH₂OH        -   C₆F₁₃CF(CF₃)CON(H)CH₂CH₂OH        -   C₇F₁₅CF(CF₃)CON(H)CH₂CH₂OH        -   C₂F₅O(C₂F₄O)₃CF₂CONHC₂H₄OH,        -   CF₃O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH,        -   C₂F₅O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH,        -   C₃F₇O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH,        -   C₄F₉O(CF(CF₃)CF₂₀)₁₋₃₆CF(CF₃)CH₂OH,        -   C₃F₇O(CF(CF₃)CF₂O)₁₂CF(CF₃)CH₂OH,        -   CF₃O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH,        -   C₂F₅O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH,        -   C₃F₇O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH,        -   C₄F₉O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH,        -   n-C₄F₉OC₂F₄OCF₂CH₂OCH₂CH₂OH        -   CF₃O(CF₂CF₂O)₁₁CF₂CH₂OH,        -   CF₃CF(CF₂Cl)(CF₂CF₂)₆CF₂CON(CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₆SO₂CH₂CH₂OH,        -   CF₃(CF₂)₇SO₂CH₂CH₂OH,        -   C₅F₁₁COOCH₂CH₂OH,        -   CF₃(CF₂)₆COOCH₂CH₂OH,        -   C₆F₁₃CF(CF₃)COOCH₂CH₂CH(CH₃)OH        -   C₈F₁₇COOCH₂CH₂OH,        -   C₈F₁₇(CH₂)₁₁N(C₂H₅)CH₂CH₂OH,        -   C₃F₇CH₂OH,        -   CF₃(CF₂)₆CH₂OH,        -   Perfluoro(cyclohexyl)methanol        -   C₄F₉CH₂CH₂OH,        -   CF₃(CF₂)₅CH₂CH₂OH        -   CF₃(CF₂)₆CH₂CH₂CH₂OH,        -   CF₃(CF₂)₇CH₂CH₂OH,        -   CF₃(CF₂)₇CH₂CH₂SO₂N(CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₅CH₂CH₂SO₂N(CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₃CH₂CH₂SO₂N(CH₃)CH₂CH₂OH,        -   CF₃(CF₂)₇CH₂CH₂CH₂OH,        -   CF₃C F (CF₂H) (CF₂)₁₀(CH₂)₂OH,        -   CF₃C F (CF₂Cl) (CF₂)₁₀(CH₂)₂OH,        -   R_(f)(CH₂)₂S(CH₂)₂OH,        -   C₄F₉(CH₂)₂S(CH₂)₂OH,        -   R_(f)(CH₂)₄S(CH₂)₂H,        -   R_(f)(CH₂)₂S(CH₂)₃OH,        -   R_(f)(CH₂)₂SCH(CH₃)CH₂OH,        -   R_(f)(CH₂)₄SCH(CH₃)CH₂OH,        -   R_(f)CH₂CH(CH₃)S(CH₂)₂OH,        -   R_(f)(CH₂)₂S(CH₂)₁₁OH,        -   R_(f)(CH₂)₂S(CH₂)₃O(CH₂)₂OH,        -   R_(f)(CH₂)₃O(CH₂)₂OH,        -   R_(f)(CH₂)₃SCH(CH₃)CH₂OH,            and the like, and mixtures thereof, wherein R_(f) is a            perfluoroalkyl group of 2 to 16 carbon atoms. If desired,            rather than using such alcohols, similar thiols can be            utilized. Preferred fluorine-containing monoalcohols include            2-(N-methylperfluoro butanesulfonamido)ethanol;            2-(N-ethylperfluorobutanesulfonamido)ethanol;            2-(N-methylperfluorobutanesulfonamido)propanol;            N-methyl-N-(4-hydroxybutyl)perfluorohexanesulfonamide;            1,1,2,2-tetrahydroperfluorooctanol;            1,1-dihydroperfluorooctanol; C₆F₁₃CF(CF₃)CO₂C₂H₄CH(CH₃)OH;            n-C₆F₁₃CF(CF₃)CON(H)CH₂CH₂OH; C₄F₉OC₂F₄OCF₂CH₂OCH₂CH₂OH;            C₃F₇CON(H)CH₂CH₂OH; 1,1,2,2,3,3-hexahydroperfluorodecanol;            C₃F₇O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH;            CF₃O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH; and the like; and mixtures            thereof.

Long-chain hydrocarbon monoalcohols suitable for use in the chemicalcompositions of the present invention comprise at least one, essentiallyunbranched, hydrocarbon chain having from 10 to about 18 carbon atomswhich may be saturated, unsaturated, or aromatic. These long-chainhydrocarbon monoalcohols can be optionally substituted, for example,with groups such as one or more chlorine, bromine, trifluoromethyl, orphenyl groups. Representative long-chain hydrocarbon monoalcoholsinclude 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol,1-hexadecanol,1-octadecanol, and the like, and mixtures thereof.Preferred long-chain hydrocarbon monoalcohols have 12 to 16 carbonatoms, with 12 to 14 carbon atoms being more preferred and 12 carbonatoms being most preferred for water solubility and performance.

Silane compounds suitable for use in the chemical compositions of thepresent invention are those of the following formula (I):X—R¹¹—Si—(Y)₃  formula (I)

-   -   wherein X, R¹¹, and Y are as defined previously. Therefore,        these silane compounds contain one, two, or three hydrolyzable        groups (Y) on the silicon and one organic group including an        isocyanate-reactive or an active hydrogen reactive radical        (X—R¹¹). Any of the conventional hydrolyzable groups, such as        those selected from the group consisting of alkoxy, acyloxy,        heteroalkoxy, heteroacyloxy, halo, oxime, and the like, can be        used as the hydrolyzable group (Y). The hydrolyzable group (Y)        is preferably alkoxy or acyloxy and more preferably alkoxy.

When Y is halo, the hydrogen halide liberated from thehalogen-containing silane can cause polymer degradation when cellulosesubstrates are used. When Y is an oxime group, lower oxime groups of theformula —N═CR⁵R⁶, wherein R⁵ and R⁶ are monovalent lower alkyl groupscomprising about 1 to about 12 carbon atoms, which can be the same ordifferent, preferably selected from the group consisting of methyl,ethyl, propyl, and butyl, are preferred.

Representative divalent bridging radicals (R¹¹) include, but are notlimited to, those selected from the group consisting of —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂CH₂CH₂OCH₂CH₂—, —CH₂CH₂C₆H₄CH₂CH₂—, and—CH₂CH₂O(C₂H₄O)₂CH₂CH₂N(CH₃)CH₂CH₂CH₂—.

Other preferred silane compounds are those which contain one or twohydrolyzable groups, such as those having the structuresR¹²OSi(R¹⁷)₂R¹¹XH and (R¹⁸O)₂Si(R¹⁷)R¹¹XH, wherein R¹¹ is as previouslydefined, and R¹⁷ and R¹⁸ are selected from the group consisting of aphenyl group, an alicycylic group, or a straight or branched aliphaticgroup having from about 1 to about 12 carbon atoms. Preferably, R¹⁷ andR¹⁸ are a lower alkyl group comprising 1 to 4 carbon atoms.

Following the hydrolysis of some of these terminal silyl groups,inter-reaction with a substrate surface comprising —SiOH groups or othermetal hydroxide groups to form siloxane or metal-oxane linkages, e.g.,

can occur. Bonds thus formed, particularly Si—O—Si bonds, are waterresistant and can provide enhanced durability of the stain-releaseproperties imparted by the chemical compositions of the presentinvention.

Such silane compounds are well known in the art and many arecommercially available or are readily prepared. Representativeisocyanate-reactive silane compounds include, but are not limited to,those selected from the group consisting of:

-   -   H₂NCH₂CH₂CH₂Si(OC₂H₅)₃;    -   H₂NCH₂CH₂CH₂Si(OCH₃)₃;    -   H₂NCH₂CH₂CH₂Si(O—N═C(CH₃)(C₂H₅))₃    -   HSCH₂CH₂CH₂Si(OCH₃)₃;    -   HO(C₂H₄O)₃C₂H₄N(CH₃)(CH₂)₃Si(OC₄H₉)₃;    -   H₂NCH₂C₆H₄CH₂CH₂Si(OCH₃)₃;    -   HSCH₂CH₂CH₂Si(OCOCH₃)₃;    -   HN(CH₃)CH₂CH₂Si(OCH₃)₃;    -   HSCH₂CH₂CH₂SiCH₃(OCH₃)₂;    -   (H₃CO)₃SiCH₂CH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃;    -   HN(CH₃)C₃H₆Si(OCH₃)₃;    -   CH₃CH₂OOCCH₂CH(COOCH₂CH₃)HNC₃H₆Si(OCH₂CH₃)₃;    -   C₆H₅NHC₃H₆Si(OCH₃)₃;    -   H₂NC₃H₆SiCH₃(OCH₂CH₃)₂;    -   HOCH(CH₃)CH₂OCONHC₃H₆Si(OCH₂CH₃)₃;    -   (HOCH₂CH₂)₂NCH₂CH₂CH₂Si(OCH₂CH₃)₃    -   and mixtures thereof.

Representative examples of hydroxyl-reactive silane compounds include,but are not limited to, 3-isocyanatopropyltriethoxysilane,3-isocyanatopropyltrimethoxysilane, and the like.

The chemical compositions of the present invention optionally maycontain water-solubilizing compounds (W—H) comprising one or morewater-solubilizing groups and at least one isocyanate-reactive hydrogencontaining group. These water-solubilizing compounds include, forexample, diols and monoalcohols comprising one or morewater-solubilizing groups, added in addition to the one or more polyolsand one or more monoalcohols as described above.

The solubilizing groups of the water-solubilizing compounds include, forexample, carboxylate, sulfate, sulfonate, phosphate, phosphonate,ammonium, and quaternary ammonium groups. Such groups may be representedas —CO₂M, —OSO₃M, —SO₃M, —OPO₃M, —PO(OM)₂, —NR₂HX, —NR³X, —NRH₂X, and—NH₃X, respectively, wherein M is H or one equivalent of a monovalent ordivalent soluble cation such as sodium, potassium, calcium, and NR₃H⁺; Xis a soluble anion such as those selected from the group consisting ofhalide, hydroxide, carboxylate, sulfonates, and the like; and R isselected from the group consisting of a phenyl group, a cycloaliphaticgroup, or a straight or branched aliphatic group having from about 1 toabout 12 carbon atoms. Preferably, R is a lower alkyl group having from1 to 4 carbon atoms. The group —NR₃X is a salt of a water-soluble acid,for example trimethyl ammonium chloride, pyridinium sulfate, etc. or anammonium substituent. The group —NR₂HX is the salt of a water-solubleacid, such as dimethyl ammonium acetate or propionate. The group —NRH₂Xis the salt of a water-soluble acid, such as methyl ammonium acetate orpropionate. The group —NH₃X is the salt of a water-soluble acid, such asammonium acetate or propionate. The salt form can be made by simpleneutralization of the acid group with a base such as an amine, aquaternary ammonium hydroxide, an alkali metal carbonate or hydroxide,or the like; or alternatively by simple reaction of the amino group witha carboxylic acid, a sulfonic acid, a halo acid, or the like. Carboxylicacid groups in salt form are preferred because they have been found toimpart water solubility to the chemical compositions of the presentinvention without causing undue loss of the durable stain-releaseproperties imparted by the chemical composition.

The isocyanate-reactive hydrogen containing group is selected from thegroup consisting of —OH, —SH, NH₂, and NRH wherein R is selected fromthe group consisting of a phenyl group, a cycloaliphatic group, or astraight or branched aliphatic group having from about 1 to about 12carbon atoms. Preferably, R is a lower alkyl group having from 1 to 4carbon atoms. A representative suitable diol with a solubilizing groupis 1,1-bis(hydroxymethyl)propionic acid and its salts such as itsammonium salt. A representative suitable monoalcohol with a solubilizinggroup is glycolic acid (HOCH₂COOH) and its salts. The amount ofwater-solubilizing group should be sufficient to solubilize the chemicalcomposition. Typically, the isocyanate:solubilizing group ratio shouldbe from about 3:1 to about 16:1, preferably from about 5:1 to about11:1. Illustrative water-solubilizing compounds having suitablewater-solubilizing groups include, but are not limited to, thoseindependently selected from the group consisting of HOCH₂COOH;HSCH₂COOH; (HOCH₂CH₂)₂NCH₂COOH; HOC(CO₂H)(CH₂CO₂H)₂;(H₂N(CH₂)_(n)CH₂)₂NCH₃ wherein n is an integer of 1 to 3;(HOCH₂)₂C(CH₃)COOH; (HO(CH₂)_(n)CH₂)₂NCH₃ wherein n is an integer of 1to 3; HOCH₂CH(OH)CO₂Na; N-(2-hydroxyethyl)iminodiacetic acid(HOCH₂CH₂N(CH₂COOH)₂); L-glutamic acid (H₂NCH(COOH)(CH₂CH₂COOH));aspartic acid (H₂NCH(COOH)(CH₂COOH)); glycine (H₂NCH₂COOH);1,3-diamino-2-propanol-N,N,N′,-tetraacetic acid (HOCH(CH₂N(CH₂COOH)₂)₂);iminodiacetic acid (HN(CH₂COOH)₂); mercaptosuccinic acid(HSCH(COOH)(CH₂COOH)); H₂N(CH₂)₄CH(COOH)N(CH₂COOH)₂;HOCH(COOH)CH(COOH)CH₂COOH; (HOCH₂)₂CHCH₂COO)⁻(NH(CH₃)₃)⁺;CH₃(CH₂)₂CH(OH)CH(OH)(CH₂)₃CO₂K; H₂NCH₂CH₂OSO₃Na; H₂NC₂H₄NHC₂H₄SO₃H;H₂NC₃H₆NH(CH₃)C₃H₆SO₃H; (HOC₂H₄)₂NC₃H₆OSO₃Na;(HOCH₂CH₂)₂NC₆H₄OCH₂CH₂OSO₂OH;N-methyl-4-(2,3-dihydroxypropoxy)pyridinium chloride,((H₂N)₂C₆H₃SO₃)⁻(NH(C₂H₅)₃)⁺; dihydroxybenzoic acid;3,4-dihydroxybenzylic acid; 3-(3,5-dihydroxyphenyl)propionic acid; saltsof the above amines, carboxylic acids, and sulfonic acids; and mixturesthereof.

The stain release compositions of the present invention can be madeaccording to the following step-wise synthesis. As one skilled in theart would understand, the order of the steps is non-limiting and can bemodified so as to produce a desired chemical composition. In thesynthesis, the polyfunctional isocyanate compound and the polyol aredissolved together under dry conditions, preferably in a solvent, andthen heating the resulting solution at approximately 40 to 80° C.,preferably approximately 60 to 70° C., with mixing in the presence of acatalyst for one-half to two hours, preferably one hour. Depending onreaction conditions (e.g., reaction temperature and/or polyfunctionalisocyanate used), a catalyst level of up to about 0.5 percent by weightof the polyfunctional isocyanate/polyol mixture may be used, buttypically about 0.00005 to about 0.5 percent by weight is required, 0.02to 0.1 percent by weight being preferred. Suitable catalysts include,but are not limited to, tertiary amine and tin compounds.

Examples of useful tin compounds include tin II and tin IV salts such asstannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltindi-2-ethylhexanoate, and dibutyltinoxide. Examples of useful tertiaryamine compounds include triethylamine, tributylamine,triethylenediamine, tripropylamine, bis(dimethylaminoethyl) ether,morpholine compounds such as ethyl morpholine, and2,2′-dimorpholinodiethyl ether, 1,4-diazabicyclo[2.2.2]octane (DABCO,Sigma-Aldrich Chemical Co., Milwaukee, Wis.), and1,8-diazabicyclo[5.4.0.]undec-7-ene (DBU, Sigma-Aldrich Chemical Co.,Milwaukee, Wis). Tin compounds are preferred.

A mixture of polyols can be used instead of a single polyol. Forexample, in a preferred embodiment a polyol mixture comprising a polyolwith a water-solubilizing group and a polyol with an R_(f) group isused. When the polyfunctional isocyanate compound is a triisocyanate,the polyol is preferably a diol to prevent undesired gelation, which canoccur when polyols having three or more hydroxyl groups are reacted witha triisocyanate.

The resulting isocyanate functional urethane oligomers and compounds arethen further reacted with one or more of the monoalcohols describedabove. The monoalcohol(s) is (are) added to the above reaction mixture,and react(s) with a substantial portion of the remaining NCO groups. Theabove temperatures, dry conditions, and mixing are continued one-half totwo hours, preferably one hour. Terminal fluorine-containing and/orlong-chain hydrocarbon groups are thereby bonded to the isocyanatefunctional urethane oligomers and compounds. These oligomers andcompounds are further functionalized with silane groups described aboveby reacting any of the remaining NCO groups in the resulting mixturewith one or more of the reactive hydrogen-containing silane compoundsdescribed above. Thus, the silane compound(s) is (are) added to thereaction mixture, using the same conditions as with the previousadditions. Aminosilanes are preferred, because of the rapid and completereaction that occurs between the remaining NCO groups and the silanecompound's amino groups. Isocyanato functional silane compounds may beused and are preferred when the ratio of polyfunctional isocyanatecompound to the polyol and monoalcohol is such that the resultingoligomer has a terminal hydroxyl group.

Water-solubilizing compounds can be added and reacted with NCO groupsunder the conditions described above in any of the steps describedabove. For example, as mentioned above, the water-solubilizing compoundcan be added as a mixture with the polyol. Alternatively, thewater-solubilizing compound can be added (a) after reaction of thepolyol with the polyfunctional isocyanate, (b) as a mixture with themonoalcohol(s), (c) after reaction of the polyol and monoalcohol withthe polyfunctional isocyanate, (d) as a mixture with the silane, and (e)after the reaction of the polyol, monoalcohol, and silane with thepolyfunctional isocyanate. When the water-solubilizing compound is amonoalcohol, it is preferably added as a mixture with thefluorine-containing monoalcohol or the long-chain hydrocarbonmonoalcohol. When the water-solubilizing compound is a diol, it ispreferably added as a mixture with the polyol.

When the chemical composition of the present invention contains aurethane oligomer having one or more carboxylic acid groups, solubilityof the composition in water can be further increased by forming a saltof the carboxylic acid group(s). Basic salt-forming compounds, such astertiary amines, quaternary ammonium hydroxides, and inorganic bases,including, but not limited to, those selected from the group consistingof sodium hydroxide, potassium hydroxide, cesium hydroxide, lithiumhydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, andbarium hydroxide, may be used in a sufficient amount (i.e., in an amountto maintain a pH of greater than about 6). These basic salt-formingcompounds preferably can be added in the water phase, but optionally inthe preparation of the urethane oligomers, to form salts with theincorporated, pendant and/or terminal carboxylic acid groups on theurethane oligomer. Examples of useful amine salt-forming compoundsinclude, but are not limited to, those selected from the groupconsisting of ammonia, trimethylamine, triethylamine, tripropylamine,triisopropylamine, tributylamine, triethanolamine, diethanolamine,methyldiethanolamine, morpholine, N-methylmorpholine,dimethylethanolamine, and mixtures thereof. Preferred salt formingcompounds include those selected from the group consisting of ammonia,trimethylamine, dimethylethanolamine, methyldiethanolamine,triethylamine, tripropylamine, and triisopropylamine, since the chemicalcompositions prepared therefrom are not excessively hydrophilic uponcoating and curing. Since certain salts formed by the reaction of saltforming compounds, such as potassium hydroxide in combination with acarboxylic acid group, could result in undesired reaction with NCOgroups, it is preferred to add the salt forming compound in a waterphase after all of the diols, alcohol, and silane compounds have beenreacted with the NCO groups of the polyfunctional isocyanate compound.

The molar ratios of the components of the chemical composition of thepresent invention are as follows:

-   -   one or more polyfunctional isocyanate compounds and one or more        polyols are used in a molar ratio of from about 1:0.25 to about        1:0.45;    -   one or more polyfunctional isocyanate compounds and one or more        monoalcohols (as discussed above) are used in a molar ratio of        from about 1:0.30 to about 1:0.60;    -   one or more polyfunctional isocyanate compounds and one or more        silanes (of formula I above) are used in a molar ratio of from        about 1:0.001 to about 1:0.15; and    -   one or more polyfunctional isocyanate compounds and one or more        water-solubilizing compounds (as discussed above) are used in a        molar ratio of from about 1:0 to about 1:1.6.        The preferred molar ratios are as follows:    -   one or more polyfunctional isocyanate compounds and one or more        polyols are used in a molar ratio of from about 1:0.35 to about        1:0.42;    -   one or more polyfunctional isocyanate compounds and one or more        monoalcohols (as discussed above) are used in a molar ratio of        from about 1:0.45 to about 1:0.55;    -   one or more polyfunctional isocyanate compounds and one or more        silanes (of formula I above) are used in a molar ratio of from        about 1:0.03 to about 1:0.08; and    -   one or more polyfunctional isocyanate compounds and one or more        water-solubilizing compounds (as discussed above) are used in a        molar ratio of from about 1:0 to about 1:1.0.

EXAMPLES

Formulation and Treatment Procedure for Textile Substrates:

Treatment baths were formulated containing a defined amount of thefluorochemical polymer. Treatments were applied to the test substratesby padding to provide a concentration as indicated in the examples(based on fabric weight and indicated as SOF (solids on fabric)).Samples were air dried at ambient temperature for 24-48 hours followedby conditioning at 21° C. and 50% relative humidity for 2 hours (aircure). Alternatively, the samples were dried and cured at 160° C. during1.5 minutes or at 150° C. during 10 minutes, as indicated in theexamples.

After drying and heat cure, the substrates were tested for theirrepellency properties.

Formulation and Treatment Procedure for Carpet:

Treatment baths were formulated containing a defined amount of thefluorochemical compound. Treatments were applied to carpet by sprayapplication to provide 30% wet pick up (WPU). Treated samples were driedat 120° C. during 15-20 min. After drying, the treated carpet substrateswere tested for their repellency properties.

Substrates used for the evaluation of treatments of this invention werecommercially available and are listed below:

-   -   IND: “Imported Nexday Twill” 100% ring spun cotton, dyed        unfinished from Avondale mills in Graniteville S.C., USA;    -   SHIPP: “Super Hipagator” 100% ring/OE spun cotton, dyed        unfinished from Avondale Mills in Graniteville S.C., USA;    -   K-2: A 65% polyester, 35% cotton woven twill fabric (8.5        ounces/yd² (271 grams/square meter) basis wt; available from        Avondale Mills, Graniteville, S.C.)    -   TCIK: Tan 100% Cotton Interlock Knit (9.5 ounces/yd²), dyed        unfinished; available from Majestic Laces Ltd., Toronto, CA.    -   TCTK: tan 100% Cotton Thermal Underwear Knit (approximately 9.0        ounces/yd²), dyed unfinished; available from Majestic Laces        Ltd., Toronto, CA.    -   PES/Co (2681.4): polyester/cotton 65/35 fabric, style no.        2681.4, available from Utexbel N.V., Ronse, Belgium;    -   PAμ (7819.4): 100% polyamide microfiber, style no. 7819.4,        available from Sofinal, Belgium;    -   Co (1511.1): 100% cotton: bleached, mercerized cotton poplin,        style no. 1511.1, available from Utexbel N.V., Ronse, Belgium;    -   PESμ (6145.3): 100% polyester microfiber, style no. 6145.3,        available from Sofinal, Belgium;    -   Reeve: 50/50 polyester cotton; available from Reeve,        Bishopville, N.C.;    -   NS1: white polyamide carpet (level loop), 500 g/m², available        from Associated Weavers, Belgium; and    -   NS2: white polyamide carpet (cut pile), 700 g/m², available from        Associated Weavers, Belgium.

Respective data of water and oil repellency shown in the Examples andComparative Examples were based on the following methods of measurementand evaluation criteria:

Spray Rating (SR)

The spray rating of a treated substrate is a value indicative of thedynamic repellency of the treated substrate to water that impinges onthe treated substrate. The repellency was measured by Standard TestNumber 22, published in the 1985 Technical Manual and Yearbook of theAmerican Association of Textile Chemists and Colorists (AATCC), and wasexpressed in terms of ‘spray rating’ of the tested substrate. The sprayrating was obtained by spraying 250 ml water on the substrate from aheight of 15 cm. The wetting pattern was visually rated using a 0 to 100scale, where 0 means complete wetting and 100 means no wetting at all.

Water Repellency Test (WR)

The water repellency (WR) of a substrate was measured using a series ofwater-isopropyl alcohol test liquids and was expressed in terms of the“WR” rating of the treated substrate. The WR rating corresponded to themost penetrating test liquid that did not penetrate or wet the substratesurface after 10 seconds exposure. Substrates which were penetrated by100% water (0% isopropyl alcohol), the least penetrating test liquid,were given a rating of 0; substrates resistant to 100% water were givena rating W and substrates resistant to 100% isopropyl alcohol (0%water), the most penetrating test liquid, were given a rating of 10.Other intermediate ratings were calculated by dividing the percentisopropylalcohol in the test liquid by 10, e.g., a treated substrateresistant to a 70%/30% isopropyl alcohol/water blend, but not to an80%/20% blend, would be given a rating of 7.

Oil Repellency (OR)

The oil repellency of a substrate was measured by the AmericanAssociation of Textile Chemists and Colorists (AATCC) Standard TestMethod No. 118-1983, which test was based on the resistance of a treatedsubstrate to penetration by oils of varying surface tensions. Treatedsubstrates resistant only to NUJOL® mineral oil (the least penetratingof the test oils) were given a rating of 1, whereas treated substratesresistant to heptane (the most penetrating of the test liquids) weregiven a rating of 8. Other intermediate values were determined by use ofother pure oils or mixtures of oils, as shown in the following table.

Standard Test Liquids AATCC Oil Repellency Rating Number Compositions 1NUJOL ® 2 NUJOL ® /n-Hexadecane 65/35 3 n-Hexadecane 4 n-Tetradecane 5n-Dodecane 6 n-Decane 7 n-Octane 8 n-Heptane

Bundesmann Test

The impregnating effect of rain on treated substrates was determinedusing the Bundesmann Test Method (DIN 53888).

In this test, the treated substrates were subjected to a simulatedrainfall, while the back of the substrate was being rubbed. Theappearance of the upper exposed surface was checked visually after 1, 5and 10 minutes and was given a rating between 1 (complete surfacewetting) and 5 (no water remained on the surface). Besides theobservation of the wetting pattern, also the water absorption (% abs)was measured. Well treated samples gave low absorption results.

Laundering Procedure 1 (HL Ironing)

The procedure set forth below was used to prepare treated substratesamples designated in the examples below as “5 Home Launderings—Ironing(5HL—Ironing)”. A sheet of treated substrate (generally square 400 cm²to about 900 cm²) was placed in a washing machine (Miele W 724) alongwith a ballast sample (at least 1.4 kg of 90×90 cm² hemmed pieces ofapproximately 250 g/m unfinished sheeting substrate, either cotton or50/50 polyester/cotton, available from Test Fabrics, Inc., New Jersey,USA). The total weight of the treated substrates and ballast should be1.8+/−0.2 kg. 60 g IEC Test Detergent with perborate, Type I (availablethrough common detergent suppliers) was added and the washer was filledwith 30 l water. The water was heated to 40° C.+/−3° C. The substrateand ballast load were washed 5 times, followed by five rinse cycles andcentrifuging. The samples were not dried between repeat cycles. Afterthe washes, the treated substrate and dummy load were dried together ina dryer at 65° C., for 45+−5 minutes. After drying, the treatedsubstrate was pressed for 15 seconds, using an iron set at a temperatureof 150-160° C.

Laundering Procedure 2 (HL)

The procedure set forth below was used to prepare treated substratesamples designated in the examples below as “5 Home Launderings (5HL)”.

A 230 g sample of generally square, 400 cm² to about 900 cm² sheets oftreated substrate was placed in a washing machine along with a ballastsample (1.9 kg of 8 oz fabric in the form of generally square, hemmed8100 cm² sheets). A commercial detergent (“Tide Ultra Liquid” deepcleaning formula, available from Proctor and Gamble, 90 g) was added andthe washer was filled to high water level with hot water (41° C.+−2°C.). The substrate and ballast load were washed five times using a12-minute normal wash cycle.

The substrate and ballast were dried together in a conventional tumbledrier at 65+−5° C. during 45+−5 minutes. Before testing, the substrateswere conditioned at room temperature during about 4 hours.

10 HL (10 Home Launderings) or 20 HL (20 Home Launderings) indicatedthat the substrate was washed 10 or 20 times respectively according tothe procedure above.

Accelerated Dry Soil Test (ADS)

The accelerated dry soil test measures the tendency of a substrate toresist dry soil during use. A total of four treated samples, sized 14cm×17 cm were soiled in an Accelerated Soil Tester (available fromCustom Scientific Instrument, New Jersey), filled with 60 steel balls(1.27 cm diameter), using 3M Standard Carpet Dry Soil (available from3M, Order No. SPS-2001) during a ten minute run. After removal of thesamples from the soil tester, the excess soil was removed by blowingwith compressed air. Evaluations were made by comparing to a 3M SoilResistance Rating Board (available from 3M, Order No. SPS-1006) in an“Evaluation Area” (as indicated in AATCC Test Method 124-1984) with an“Overhead Lighting Arrangement” (as indicated in AATCC Test Method124-1984, section 4.3 and FIG. 1). A dry soil rating of 5 indicated thatthere was no increase in soiling versus a blank, a dry soil rating of 1refers to severe soiling.

Stain Release Test

This test evaluates the release of forced-in oil-based stains from thetreated fabric surface during simulated home laundering. Five drops ofmineral oil, Stain K (Kaydol, Witco Chemical Co.) are dropped onto thefabric surface in a single puddle, and a separate puddle of 5 drops ofMAZOLA™ corn oil, Stain E, are dropped on the fabric, and in a thirdpuddle, 5 drops of dirty motor oil, Strain C, (3M Co.) are dropped ontothe fabric. The puddles are covered with glassine paper, and weightedwith a five-pound weight each for 60 seconds. The weights and glassinepaper are removed from the fabric. The fabric sample is hung for 15-60minutes, and then washed and dried. Samples are evaluated against arating board, and assigned a number from 1 to 8. An 8 represents totalremoval of the stain, where 1 is a very dark stain. A more detaileddescription of the test is written in the 3M Protective MaterialDivision's “Stain Release Test I” method (Document # 98-0212-0725-7).

Application of Compositions to Polyester/Cotton Woven Fabrics (TreatingFabrics)

A 65% polyester, 35% cotton woven twill fabric (8.5 ounces/yd² (271grams/square meter) basis wt; available from Avondale Mills,Graniteville, S.C.) was dipped into a bath of the diluted chemicalcomposition and immediately sent through a nip. The concentration of thebath was adjusted to produce a fabric that when dry had a fluorochemicalsolids coating ranging from 0.2 to 1.0% solids on the fabric totalweight. The bath also contained a glyoxal-type resin, PERMAFRESH™ ULF(Omnova Solutions, Inc., Chester, S.C.), at about 12% on the weight ofthe bath, a citric acid activated magnesium chloride catalyst, CATALYST™531 (Omnova Solutions, Inc.), at about 3.0% on the weight of the bath,and a nonionic surfactant, PAT-WET™ LF-55 (Yorkshire Pat-Chem Inc.,Greenville, S.C.), at about 0.1% on the weight of the bath. The fabricwas dried and cured for 10 minutes at 150° C. Various performance testswere run on the fabric.

Application of Compositions to Cotton/Polyester Knit Fabric (TreatingFabrics)

Knit fabrics (100% cotton knit) were treated in the same way as thewoven fabrics, with the exception that FREEREZ™ 845 (Noveon, Inc.,Cleveland, Ohio), a pre-catalyzed glyoxal-type resin, was used in placeof the resin and catalyst combination above (Test Method IV), at about12% on the weight of the bath.

Descriptor Formula/Structure Availability AC-600 FLUOWET ™ AC-600;C₆F₁₃C₂H₄O₂CCH═CH₂ Clariant, Charlotte, NC AIBN AzobisisobutyronitrileSigma-Aldrich, Milwaukee, WI APTES 3-Aminopropyltriethoxysilane;Sigma-Aldrich H₂NCH₂CH₂CH₂Si(OCH₂CH₃)₃ ARQUAD ™ 12-50 dodecyl trimethylammonium chloride Akzo, Netherlands DBTDL Dibutyl tin dilaurateSigma-Aldrich DDI 1410 dimer diisocyanate Henkel, Düsseldorf, GermanyDes N-100 DESMODUR ™ N 100; Polyfunctional Bayer, Pittsburgh. PAisocyanate resin based on hexamethylene diisocyanate; eq wt = 191;—NCO_(avg)/molecule > 3.0 Des N-3300 DESMODUR ™ N 3300; PolyfunctionalBayer isocyanate resin based on hexamethylene diisocyanate; eq wt = 194;—NCO_(avg)/molecule > 3.0 Des W DESMODUR ™ W; methylene bis(4- Bayercyclohexyl isocyanate) EA-600 FLUOWET ™ EA-600; C₆F₁₃C₂H₄OH Clariant,Charlotte,NC Sermul ™ EA 266 C₁₃— alcohol polyethylene glycol ether(15EO) Sasol, Germany sulphate, Na salt ETHOQUAD ™ 18/25 methylpolyoxyethylene(15)octadecyl Akzo ammonium chloride FBSEEC₄F₉SO₂N(CH₂CH₂OH)₂ FLUOWET ™ EA 812 C_(n)F_(2n+1)CH₂CH₂OH(n_(avg)~9)Clariant GMS Glycerol monostearate Acme-Hardesty, Santa Barbara, CAHFE-7100 Perfluorobutyl methyl ether 3M, StPaul, MN Isofol 18T2-alkylalkanol Condea, Germany IPDI Isophorone diisocyanate Merck KGaA,Darmstadt, Germany MPEG-750 methoxypolyethylene glycol (MW 750) UnionCarbide, Danbury, CT MEKO CH₃C(═NOH)C₂H₅ Sigma-Aldrich MIBK Methylisobutyl ketone; 4-methyl-2-pentanone Sigma-Aldrich MONDUR ™ MR Aromaticpolymeric isocyanate based on Bayer diphenylmethane-diisocyanate ODIOctadecyl isocyanate; CH₃(CH₂)₁₇NCO Sigma-Aldrich PAPI VORANATE ™ M220:polymethylene Dow Chemical, polyphenyl isocyanate Midland, MIPoly(styrene-co-allyl [CH₂CH(C₆H₅)]_(x)[CH₂CH(CH₂OH)]_(y) Sigma-Aldrichalcohol) M_(n) = 1200, MW_(avg) = 2200 Rewopon ™ IM/OA imidazoline typesurfactant Rewo TOLONATE ® HDT Tris(6-isocyanatohexyl)isocyanurateRhodia UNILIN ™ 350 Polyethylene alcohol; MW_(avg) = 350 Baker,Petrolite; Tulsa, OK

-   (HFPO)_(k)-alc: HFPO oligomer alcohols,    CF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(n)CF(CF₃)CONHCH₂CH₂OH, consisting of a    mixture of oligomers with different chain lengths. The indexes k and    n are indicative of the mathematical average of the number of    repeating HFPO-units and k=n+2. The percentage of oligomeric    alcohols with a fluorinated polyether group having a molecular    weight lower than 750 g/mol was 3.2% for (HFPO)_(11.5)-alc, 0% for    (HFPO)_(10.7)-alc and (HFPO)_(9.7)-alc; 5.7% for (HFPO)_(8.8)-alc    and 15.9% for (HFPO)_(5.5)-alc.-   (HFPO)_(k)-diol: HFPO oligomer diol,    CF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(n)CF(CF₃)CONHCH₂CH(OH)CH₂OH, consisting    of a mixture of oligomers with different chain lengths. The indexes    k and n are indicative of the mathematical average of the number of    repeating HFPO-units and k=n+2. The percentage of oligomeric    alcohols with a fluorinated polyether group having a molecular    weight lower than 750 g/mol was 5.7% for (HFPO)_(8.8)-diol.-   MeFBSE: C₄F₉SO₂N(CH₃)CH₂CH₂OH, can be prepared according to WO    01/30873, Ex 2 Part A.-   FBSEE: C₄F₉SO₂N(CH₂CH₂OH)₂-   MeFBSEA: C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂, can be prepared according    to WO 01/30873, Ex 2 Part A & B.-   (4-1)MeFBSEA-ol: oligomer alcohol MeFBSEA/2-mercaptoethanol 4/1,    prepared according to U.S. Pat. No. 6,239,247 B1, column 12, lines    50-59.-   (4-1)MeFBSEA-diol: oligomer diol MeFBSEA/3-mercapto 1,2-propane diol    4/1, prepared according to U.S. Pat. No. 6,239,247 B1, column 12,    lines 50-59-   (4-1)ODA-ol: oligomer alcohol octadecylacrylate/2-mercaptoethanol    4/1, prepared according to U.S. Pat. No. 6,239,247 B1, column 12,    lines 50-59    Aldrich Chemical Co.-   (4-1)AC 600-ol: oligomer alcohol, prepared from FLUOWET™ AC    600/2-mercaptoethanol 4/1, according to U.S. Pat. No. 6,239,247 B1,    column 12, lines 50-59, except that AIBN was used and the reaction    was run at 75° C. during 15 hours.

A. Synthesis of HFPO-oligomer Alcohol and Diol

1. Synthesis of HFPO-oligomer Alcohol ((HFPO)_(k)-alc

Several HFPO-oligomer alcohols ((HFPO)_(k)-alc) were prepared accordingto the general procedure as given for the synthesis ofCF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(6.8)CF(CF₃)CONHCH₂CH₂OH, indicated in table 1as (HFPO)_(8.8)-alc.

A 1 liter 3-necked reaction flask was equipped with a stirrer, acondenser, a dropping funnel, a heating mantle and a thermometer. Theflask was charged with 1000 gCF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(6.8)CF(CF₃)COOCH₃. The mixture was heated to40° C. and 43.4 g ethanolamine was added via the dropping funnel, over aperiod of 30 minutes. The reaction mixture was kept at 65° C. during 3hours. FTIR analysis indicated complete conversion. The end productcould be purified as follows: 500 ml ethylacetate were added and theorganic solution was washed with 200 ml HCL (1N), followed by 2 washingswith 200 ml brine. The organic phase was dried over MgSO₄. Ethylacetatewas evaporated with waterjet vacuum, using a Büchi rotary evaporator.The product was dried at 50° C. during 5 hours, using oil pump vacuum(<1 mbar). An alternative purification step included evaporation ofmethanol, formed during reaction, via water jet vacuum, using a Büchirotary evaporator (up to 75° C.=<100 mm Hg). Residual methanol wasfurther removed with oil pump vacuum (up to 80° C., =<10 mbar).

The HFPO-oligomer alcohol (HFPO)_(8.8)-alc obtained, was a yellowcoloured oil, with medium viscosity. The structure was confirmed bymeans of NMR.

HFPO-oligomer alcohols with other chain lengths were preparedessentially according to the same procedure.

2. Synthesis of HFPO-oligomer diol ((HFPO)_(k)-diol))

CF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(6.8)CF(CF₃)CONHCH₂CH(OH)CH₂OH, indicated as(HFPO)_(8.8)-diol was prepared starting fromCF₃CF₂CF₂—O—(CF(CF₃)CF₂O)_(6.8)CF(CF₃)COOCH₃, using the followingprocedure:

A round bottom flask, equipped with a stirrer, a nitrogen inlet and atemperature control was charged with 147.6 gCF₃CF₂CF₂—O—(CF(CF₃)CF₂₀)_(6.8)CF(CF₃)COOCH₃ and 9.57 g3-amino-1,2-propanediol. The reaction mixture was stirred while heatingto 50° C. An exothermic reaction was noticed (up to 70° C.). Thereaction was continued during 24 hours. FTIR analysis indicated completeconversion of the methylester function. The reaction product wasdissolved in a mixture of MIBK/acetone/HFE 7100 (100 g/100 g/75 g) andwashed 2 times with a solution of 5% HCl and two times with water. Phaseseparation occurred at 65° C. The solvent phase was dried oversodiumsulfate and the solvents were removed by evaporation. Thestructure of the (HFPO)_(8.8)-diol was confirmed by FTIR.

B. Synthesis of FC Polyether Urethanes

1. Synthesis of FC Polyether Urethanes Starting from HFPO-oligomerAlcohol

a. Fluorochemical Polyether Urethane Derivatives FC-UR1 to FC-UR3 andFC-UR9 to FC-UR12.

Fluorochemical polyether urethane derivatives FC-UR1 to FC-UR3 andFC-UR9 to FC-UR12, as given in table 1, were made according to thesynthesis of FC-UR1: (HFPO)_(8.8)-alc/PAPI/MEKO (1/1/2)

In a first step, 20 g (HFPO)_(8.8)-alc was charged into a 3-neckedreaction flask, equipped with a magnetic stirring bar, a condenser, athermometer, a heating mantle and a nitrogen inlet. 38.5 g ethylacetateand 3 g HFE-7100 were added to obtain a clear solution. 5.4 g PAPI wereadded, followed by a slow addition of 2.3 g MEKO (through a syringe).The reaction was run at 75° C. during 6 hours. An additional 0.46 g MEKOwas added and the reaction was continued at 75° C. during 6 hours. FTIRanalysis indicated complete conversion.

FC-UR2 to FC-UR3 and FC-UR9 to FC-UR12 were made essentially accordingto the same procedure, except that no HFE-7100 was used and 2 dropsDBTDL catalyst were added.

In a second step, the fluorochemical polyether urethane derivatives wereemulsified. The reaction mixture was dispersed in water containingETHOQUAD 18/25 (5% on solids) using a Branson 450 sonifier (2′ u-soundat 65° C.). The solvent was stripped off with waterjet vacuum, using aBüchi rotary evaporator. Stable milky dispersions were obtained.

b. Fluorochemical Polyether Urethane FC-UR4 and Comparative UrethanesC-UR1 to C-UR4.

For the synthesis of FC-UR4 and C-UR1 to C-UR4, 250 ml polymerisationflasks were charged with the reactants in amounts to provide a molarratio as given in table 1. Ethyl acetate was added to obtain 40% solidssolutions. The reaction flasks were sealed after purging with nitrogenand the reactions were run in a preheated Launder-o-meter, set at 80°C., overnight. FT-IR analysis indicated complete conversion. Thefluorochemical polyether urethanes were emulsified as described above,using a mixture of ETHOQUAD™18/25 (2.5% on solids) and ARQUAD™ 12-50(2.5% on solids) or using Sermul™ EA266 (7% on solids).

c. Fluorochemical Polyether Urethane Derivatives FC-UR5 to FC-UR8

Three-necked round bottom flasks were charged with the reactants inmolar ratios as given in Table 1. Ethyl acetate was added to obtain ˜50%solids solutions and one drop of DBTDL was added. The flasks weresealed, purged with nitrogen, and heated at 75° C. overnight. (Note: Forthe preparation of FC-UR5 and FC-UR6 MEKO was added at this point in themolar ratios given in Table 1 and the mixture was reheated to 75° C. andallowed to stir for 4 additional hours.) A 3% aqueous solution ofETHOQUAD™ 18/25 (˜10% on solids) was slowly added to the mixture keepingthe temperature >60° C. during addition. The mixture was sonified with aColeParmer model CPX-600 ultrasonic processor for 5 minutes. Ethylacetate was removed by distillation under reduced pressure on a Büchirotary evaporator.

d. Fluorochemical Polyether Urethane Derivatives FC-UR41 and FC-UR42

A reaction flask was charged with 100 g ααα-trifiuorotoluene, Des N-3300and (HFPO)_(5.5)-alc in amounts to provide the molar ratio as given inTable 1. 1 drop of DBTDL was added and the mixture was heated at 95° C.during 1 hour. (4-1)ODA-ol (FC-UR41) or polystyrene-coallyl alcohol(FC-UR42) were added and the mixture was heated at 75° C. during 12hours. FT-IR analysis indicated complete conversion.

In a second step, the fluorochemical polyether urethanes wereemulsified. The reaction mixtures were dispersed in water containingETHOQUAD™ 18/25 (5% on solids) using a Branson 450 sonifier (4 minu-sound at 65° C.). The solvent was stripped with a water jet aspiratorusing a Büchi rotary evaporator. Stable milky dispersions were obtained.

e. Fluorochemical Polyether Urethane FC-UR43

In a first step, a 3-necked reaction flask, equipped with a magneticstirring bar, a condenser, a thermometer, a heating mantle and anitrogen inlet was charged with 59.6 g (HFPO)_(10.7)-alc, 4.9 g1-C₁₈H₃₇OH, 27.6 g Tolonate® HDT and 133 g 4-methyl-2-pentanone undernitrogen. The reaction mixture was heated to 85° C. and 0.1 g DBTDL wasadded. The reaction was run under nitrogen atmosphere, at 85° C. during3 hours. 7.9 g MEKO were added and the reaction was stirred overnight at85° C., under nitrogen. A solution of 16.7 g 30% aqueous ETHOQUAD™ 18/25in 388.4 g DIW was slowly added to the reaction mixture, keeping thetemperature >=80° C. The mixture was sonified using a Cole-Parmer ModelCPX 600 sonifier at a power setting of 600 W and 100% amplitude for 5minutes. The solvent was stripped off with waterjet vacuum using a Buchirotary evaporator. A stable 20% solids dispersion was obtained.

f. Fluorochemical Polyether Urethane FC-UR44

A reaction flask was charged with 50 g ααα-trifluorotoluene, Tolonate®HDT, (HFPO)8.8-alc and EA-600 in amounts to provide the molar ratio asshown in Table 1. 1 drop of DBTDL was added and the mixture was heatedat 75° C. for 2 hours. To this was added MEKO and the mixture was heatedat 75° C. for 1 hour. FT-IR analysis indicated complete conversion.

In a second step, this fluorochemical polyether urethane was emulsified.The reaction mixture was dispersed in water containing ETHOQUAD™ 18/25(5% on solids) using a Branson 450 sonifier (4 minutes u-sound at 65°C.). The solvent was stripped off with waterjet vacuum, using a Büchirotary evaporator. A stable milky dispersion was obtained.

g. Fluorochemical Polyether Urethane FC-UR46

A three-necked round bottom flask was charged with (HFPO)_(9.7)-alc(13.9 g), MONDUR™ MR (22.2 g) and MIBK (75.0 g) and heated to 75° C.under a nitrogen atmosphere. DBTDL (0.10 g) was added and the reactionmixture was held at temperature for 3 hours. MEKO (13.9 g) was slowlyadded to the reation mixture, and allowed to stir overnight at 75° C. Asolution of ETHOQUAD™ 18/25 (30% aq; 8.3 g) was slowly added to themixture, keeping the temperature >70° C. during addition. The mixturewas sonified with a Cole Parmer model CPX-600 ultrasonic processor for 5minutes. MIBK was removed by distillation under reduced pressure on aBüchi rotary evaporator.

h. Synthesis of Fluorochemical Polyether Urethane FC-UR47

To a 250 ml 3-neck flask equipped with a mechanical stirrer, condenser,thermometer, heating mantle and nitrogen inlet was charged: 8.0 g (41.88meq.) TOLONATE™ HDT, 6.25 g (2.094 meq.) MPEG 750 (25% solution in ethylacetate; pre-dried over 4A molecular sieves), 0.5565 g Stearyl alcohol(2.094 meq) and 43.4 g ethyl acetate. The mixture was heated to 68° C.under a nitrogen purge and three drops DBTDL were added. Heating wascontinued for 2 hours. A solution of 18.00 g (10.47 meq)(HFPO)_(9.1)-alc in 22.07 g ethyl acetate was prepared and added to thereaction mixture. The mixture was held at temperature for one hour andtwenty minutes. A solution of 2.37 g (27.2 meq) MEKO in 2 g ethylacetate was added, and the mixture was allowed to stir overnight at 68°C. The urethane mixture was dispersed into water with 1.52 g Ethoquad™18/25 (5% on solids) using a Cole Parmer Ultrasonic Homogenizer (for 5minutes while still hot). Ethyl acetate was removed using a rotaryevaporator. A milky dispersion was obtained.

2. Synthesis of FC Polyether Urethanes Starting from HFPO-oligomer Diol

a. Synthesis of FC Polyether Urethane (HFPO)_(8.8)-diol/GMS/PAPI/MEKO1/1/3/5 (FC-UR13)

In a first step 15.5 g (HFPO)_(8.8)-diol was charged into a 3-neckedreaction flask, equipped with a stirrer, a condenser, a thermometer, aheating mantle and a nitrogen inlet. 11.02 g PAPI, 3.6 g GMS and 4.4 gMEKO were added, followed by 52 g MIBK and 3 drops of DBTDL catalyst.The reaction was run at 75° C. during 7 hours. FTIR analysis indicatedcomplete conversion.

In a second step, the (HFPO)-urethane was emulsified. Therefore, amixture of 60 g water and 3.75 g Rewopon™ IM/OA.HAc (20% solution/5% onsolids) was made. The aqueous solution was heated at 65° C. and theorganic phase as prepared under step 1, was added under stirring. The 2phase system was emulsified using a Branson Sonifier 450W for 3 min atfull capacity. The solvent was removed by evaporation and a light brownmilky emulsion was obtained.

b. Synthesis of FC Polyether Urethanes FC-UR14 to FC-UR18

In a first step, 100 ml reaction flasks were charged with(HFPO)_(8.8)-alc, (HFPO)_(8.8)-diol and isocyanates, in amounts toprovide molar ratios as given in table 2. Ethyl acetate was added toprovide a final concentration of 40% solids. The bottles were purgedwith nitrogen and sealed. The reaction was run at 75° C. in a preheatedLaunder-o-meter, during 4 hours. GMS and MEKO were added and thereaction was run at 75° C. during 16 hours. FT-IR analysis indicatedcomplete conversion.

In a second step, the FC polyether urethanes were emulsified. Therefore,a mixture of ETHOQUAD 18/25 (5% on solids) in DI water was heated to 75°C. The FC polyether urethane solutions, prepared above, were heated to75° C. and added to the water phase while stirring. The 2 phase systemwas emulsified using a Branson Sonifier 450W for 2 min at full capacity.The solvent was removed by evaporation and stable milky dispersions wereobtained.

3. Synthesis of FC Polyether Urethanes Comprising HFPO-oligomers andFluorochemical Alkyl Derivatives

a. Synthesis of FC Polyether Urethanes FC-UR19 to FC-UR40

Fluorochemical polyether urethanes FC-UR19 to FC-UR40 were made asfollows:

In a first step, 100 ml reaction flasks were charged with(HFPO)_(8.8)-alc, (HFPO)_(8.8)-diol, MeFBSE, FBSEE, MeFBSEA oligomeralcohol and/or diol, isocyanates and blocking agents, in amounts toprovide molar ratios as given in table 1. Ethylacetate was added toprovide a concentration of 40% solids. Two drops DBTDL catalyst wereadded. The bottles were purged with nitrogen and sealed. The reactionswere run overnight at 75° C. in a preheated Launder meter. FT-IRanalysis indicated complete conversion.

In a second step, the fluorochemical polyether urethanes wereemulsified. Therefore, a 20% mixture of Rewopon™ IM/OA.Hac (Hac=aceticacid) (7% on solids) was made in water. The aqueous solution was heatedat 55° C. The organic phase as prepared under step 1, was added understirring. The two-phase system was emulsified using a Branson Sonifier450W for 3 min at full capacity. The solvent was removed by evaporationand a stable dispersion was obtained.

b. Synthesis of FC Polyether Urethane FC-UR45

A reaction flask was charged with 100 g ααα-trifluorotoluene, Tolonate®HDT, (HFPO)_(8.8)-alc and (4-1)AC 600-ol, in amounts to provide themolar ratio as shown Table 1. 1 drop of DBTDL was added and the mixturewas heated at 75° C. for 12 hours. To this was added MEKO and themixture was heated at 75° C. during 1 hour. FT-IR analysis indicatedcomplete conversion.

In a second step, this fluorochemical polyether urethane was emulsified.The reaction mixture was dispersed in water containing ETHOQUAD™ 18/25(5% on solids) using a Branson 450 sonifier (4 minutes u-sound at 65°C.). The solvent was stripped off with waterjet vacuum, using a Buchirotary evaporator. A stable milky dispersion was obtained.

c. Synthesis of FC Polyether Urethane FC-UR48

A 500 mL three-necked round bottom flask was charged with 34.8 grams(HFPO)_(9.7)-alc, 0.9 grams MeFBSE, 2.0 grams MPEG-750 and 50.0 gramsMIBK. 10.1 grams Tolonate™ HDT was then added, and the mixture washeated to 75° C. under nitrogen with stirring. Then 0.03 grams DBTDL wasadded to the cloudy mixture. An exothermic reaction began, and thetemperature rose to ˜90° C. When the exotherm subsided the reaction washeated at 75° C. for three hours. 2.3 grams MEKO was added dropwise thecontainer being rinsed in with 2 ml MIBK. The reaction was stirred at75° C. overnight under nitrogen. The next day a solution of 8.3 grams30% aqueous Ethoquad™ 18/25 in 219.2 grams DI water was added, keepingthe temperature >70° C. during addition. The ensuing mixture wassonified for five minutes. MIBK was removed by heating under reducedpressure with a Buchi rotary evaporator. This yielded a whitedispersion.

TABLE 1 composition of FC polyether urethane derivatives Molar RatioNumber Composition (equivalents) FC-UR1 (HFPO)_(8.8)-alc/PAPI/MEKO 1/1/2FC-UR2 (HFPO)_(8.8)-alc/PAPI/MEKO 2/1/1 FC-UR3 (HFPO)_(8.8)-alc/PAPI 3/1FC-UR4 (HFPO)_(8.8)-alc/Des N/C₁₆H₃₃OH 1/1/2 FC-UR5 (HFPO)_(5.5)-alc/DesN 100/MEKO (1/3/2) FC-UR6 (HFPO)_(11.5)-alc/Des N 100/MEKO (1/3/2)FC-UR7 (HFPO)_(5.5)-alc/Des N 100 3/1 FC-UR8 (HFPO)_(11.5)-alc/Des N 1003/1 FC-UR9 (HFPO)_(8.8)-alc/GMS/PAPI/MEKO 1/1/2/3 FC-UR10(HFPO)_(8.8)-alc/GMS/PAPI/MEKO 1/2/3/4 FC-UR11(HFPO)_(8.8)-alc/GMS/PAPI/MEKO 1/3/4/5 FC-UR12(HFPO)_(8.8)-alc/GMS/PAPI/MEKO 2/2/3/3 FC-UR13(HFPO)_(8.8)-diol/GMS/PAPI/MEKO 1/1/3/5 FC-UR14(HFPO)_(8.8)-alc/(HFPO)_(8.8)- 1/1/2/3 diol/PAPI/MEKO FC-UR15(HFPO)_(8.8)-alc/(HFPO)_(8.8)- 1/1/3/1/4 diol/PAPI/GMS/MEKO FC-UR16(HFPO)_(8.8)-alc/(HFPO)_(8.8)- 2/2/4/1/4 diol/PAPI/GMS/MEKO FC-UR17(HFPO)_(8.8)-alc/(HFPO)_(8.8)- 2/2/1/3/1/3 diol/DDI/PAPI/GMS/MEKOFC-UR18 (HFPO)_(8.8)-alc/(HFPO)_(8.8)- 2/2/2/3/1/5diol/DDI/PAPI/GMS/MEKO FC-UR19 (HFPO)_(8.8)-diol/FBSEE/ 1/1/3/5PAPI/MeFBSE FC-UR20 (HFPO)_(8.8)-diol/FBSEE/PAPI/ 1/1/3/3/2 MeFBSE/MEKOFC-UR21 (HFPO)_(8.8)-diol/FBSEE/ 1/1/3/5 PAPI/MEKO FC-UR22(HFPO)_(8.8)-alc/FBSEE/PAPI/ 2/4/2/5 MeFBSE FC-UR23(HFPO)_(8.8)-alc/FBSEE/PAPI/ 2/4/2/3/2 MeFBSE/MEKO FC-UR24(HFPO)_(8.8)-alc/FBSEE/PAPI/ 2/2/3/3 MeFBSE FC-UR25(HFPO)_(8.8)-alc/FBSEE/PAPI/MEKO 2/2/3/3 FC-UR26(HFPO)_(8.8)-alc/FBSEE/PAPI/MEKO 1/1/2/3 FC-UR27(HFPO)_(8.8)-alc/FBSEE/PAPI/MEKO 1/2/3/4 FC-UR28(HFPO)_(8.8)-alc/FBSEE/PAPI/MEKO 2/4/5/5 FC-UR29(HFPO)_(8.8)-alc/FBSEE/PAPI/MEKO 1/4/5/6 FC-UR30(HFPO)_(8.8)-alc/FBSEE/PAPl/MEKO 2/6/7/7 FC-UR31(HFPO)_(8.8)-alc/FBSEE/PAPI/MEKO 3/6/7/6 FC-UR32(HFPO)_(8.8)-diol/FBSEE/PAPI/ 1/3/5/7 MEKO FC-UR33(HFPO)_(8.8)-diol/(4-1)MeFBSEA- 2/2/3/3 ol/PAPI/MEKO FC-UR34(HFPO)_(8.8)-alc/(4-1)MeFBSEA- 2/2/3/3 diol/PAPI/MEKO FC-UR35(HFPO)_(8.8)-alc/(4-1)MeFBSEA- 1/0.5/1.2/3/4 diol/FBSEE/PAPI/MEKOFC-UR36 (HFPO)_(8.8)-alc/(4-1)MeFBSEA- 1/0.25/0.75/3/4diol/FBSEE/PAPI/MEKO FC-UR37 (HFPO)_(8.8)-alc/(4-1)MeFBSEA-2/0.25/1.75/3/3 diol/FBSEE/PAPI/MEKO FC-UR38(HFPO)_(8.8)-alc/(4-1)MeFBSEA- 2/1/3/5/5 diol/FBSEE/PAPI/MEKO FC-UR39(HFPO)_(8.8)-alc/(4-1)MeFBSEA- 1/0.5/2/3/3.5 ol/FBSEE/PAPI/MEKO FC-UR40(HFPO)_(8.8)-alc/(4-1)MeFBSEA- 1.5/0.5/2/3/3 ol/FBSEE/PAPI/MEKO FC-UR41(HFPO)_(5.5)-alc/Des N-3300/ 2.3/1/1 (4-1)ODA-ol FC-UR42(HFPO)_(5.5)-alc/Des N-3300/ (2/1/1) Polystyrene-coallyl alcohol FC-UR43(HFPO)_(10.7)-alc/Tolonate ® (2.5/10/1.25/6.25) HDT/C₁₈H₃₇OH/MEKOFC-UR44 (HFPO)_(8.8)-alc/Tolonate ® (1/4/1/2) HDT/EA-600/MEKO FC-UR45(HFPO)_(8.8)-alc/Tolonate ® HDT/ (1/4/1/2) (EA-600AC)₄OH/MEKO FC-UR46(HFPO)_(9.7)-alc/Mondur ™ (1/20/19) MR/MEKO FC-UR47(HFPO)_(9.1)-alc/Tolonate ™ (5/20/1/1/13) HDT/MPEG 750/Stearylalcohol/MEKO FC-UR48 (HFPO)_(9.7)-alc/Tolonate ™ (1/2.5/0.125/ HDT/MeFBSE/MPEG750/MEKO 0.125/0.125) C-UR1 MeFOSE/PAPI/MEKO 1/1/2 C-UR2 Flowet EA812/PAPI/MEKO 1/1/2 C-UR3 (HFPO)_(8.8)-alc/ODI 1/1 C-UR4(HFPO)_(8.8)-alc/DDI 1410 2/1

Examples 1 to 8

In examples 1 to 8, different substrates were treated with FC polyetherurethanes as indicated in table 2, so as to give 0.3% SOF. Aftertreatment the fabrics were dried at 160° C. during 1.5 minutes. Thetreated substrates were tested for their oil and water repellencyinitially and after 5 home launderings (ironing). The results aresummarized in Table 2.

TABLE 2 Substrates treated with FC polyether urethanes with or withoutblocking group Ex Initial 5 HL Ironing No FC-UR OR WR SR OR WR SR PESμ(6145.3) 1 FC-UR2 2 2 90 2 1 75 2 FC-UR3 3 1 70 2 0 60 PAμ (7819.4) 3FC-UR2 3 2 60 3 2 70 4 FC-UR3 3 2 50 3 1 60 PES/Co (2681.4) 5 FC-UR2 3 175 2 2 60 6 FC-UR3 3 W 0 3 0 0 Co (1511.1) 7 FC-UR2 3 1 70 2 0 60 8FC-UR3 4 0 0 1 0 0The results indicated that substrates having high and especially durableoil repellency could be made when they were treated with FC polyetherurethanes. The water repellency of the treated substrate could furtherbe increased through the use of a masking group in the FC polyetherurethane.

Examples 9 to 20

In examples 9 to 20, the influence of the add-on level of thefluorochemical polyether urethane was evaluated. Therefore, differentsubstrates were treated with FC polyether urethane FC-UR1, at differentadd on levels. After treatment the fabrics were dried and cured at 160°C. for 1.5 minutes. The treated fabrics were tested for oil and waterrepellency, initially and after home launderings (ironing). The resultsare given in Table 3.

TABLE 3 Substrates treated with FC polyether urethane FC-UR1; influenceof add-on level Ex % SOF Initial Bundesmann 5 HL ironing No FC-UR1 OR WRSR 1′ 5′ 10′ OR WR SR PESμ (6145.3) 9 0.3 1 1 95 2 1 1 0 1 75 10 0.5 1 2100 5 3 2 0 1 90 11 1 2 2 100 5 4 2 1 1 100 PAμ (7819.4) 12 0.3 3 2 70 // / 0 1 50 13 0.5 4 3 75 / / / 1 1 50 14 1 4 3 80 / / / 2 2 70 PES/Co(2681.4) 15 0.3 4 2 80 1 1 1 1 1 70 16 0.5 4 2 95 2 1 1 2 1 75 17 1 4 3100 4 2 1 3 2 90 Co (1511.1) 18 0.3 2 2 90 1 1 1 1 1 60 19 0.5 3 2 100 21 1 1 1 85 20 1 4 3 100 3 2 1 3 2 90The results indicated that the performance could be tailored byvariation of the add-on level. Substrates having high oil and/or waterrepellency with good durability could be made.

Examples 21 to 24 and Comparative Examples C-1 to C-8

In examples 21 to 24, substrates were treated with FC-UR1, and withcomparative FC urethanes, made from long chain FC alkyl alcohols. Thesubstrates were treated so as to give 0.3% SOF. After treatment, thesubstrates were dried and cured at 160° C., during 1.5 min. The resultsof oil and water repellency are given in table 4.

TABLE 4 substrates treated with FC polyether urethane Ex InitialBundesmann 5 HL Ironing No FC-UR OR WR SR 1′ 5′ 10′ % abs OR WR SR PESμ(6145.3) 21 FC-UR1 2 2 100 4 2 1 12.1 0 1 85 C-1 C-UR1 1 2 100 4 2 1 120 2 90 C-2 C-UR2 2 3 100 5 4 4 4.4 0 2 90 PAμ (7819.4) 22 FC-UR1 3 1 50/ / / / 2 2 60 C-3 C-UR1 3 7 90 1 1 1 25.9 0 2 70 C-4 C-UR2 4 7 100 2 11 24.8 1 2 75 PES/Co (2681.4) 23 FC-UR1 4 2 90 1 1 1 23.3 1 2 75 C-5C-UR1 3 3 100 4 2 1 18.8 1 2 80 C-6 C-UR2 5 6 100 5 4 4 11.2 1 3 85 Co(1511.1) 24 FC-UR1 4 2 90 1 1 1 32.6 2 1 70 C-7 C-UR1 3 4 100 4 1 1 25.91 2 80 C-8 C-UR2 4 4 100 5 3 1 23.5 2 2 80The results indicated that most substrates, treated with FC polyetherurethanes according to the invention, had the same good initial andbetter durable oil repellency, compared to substrates treated with FCurethanes, made from long chain FC alcohols. A further advantage couldbe seen in that the substrates treated with FC polyether urethanes had asofter feel than the substrates treated with the comparative urethanes.

Examples 25 to 31 and Comparative Examples C-9 to C-16

In examples 25 to 31, the influence of the functionality of theisocyanate used in the synthesis of the fluorochemical polyetherurethane was evaluated. Substrates were treated with aliphatic urethaneFC-UR4, made with triisocyanate Des N-100. In comparative examples C-9to C-16, substrates were treated with the comparative urethanes C-UR3and C-UR4, made from FC polyether oligomer and diisocyanates. Allsubstrates were treated so as to give 0.3% SOF. After treatment, thesubstrates were dried and cured at 160° C. during 1.5 min. Oil and waterrepellency were evaluated. The results are given in Table 5.

TABLE 5 Ex Initial 5 HL Ironing No FC-UR OR WR SR OR WR SR PESμ (6145.3)25 FC-UR4 2 2 70 1 0 50 C-9 C-UR3 0 1 0 0 0 0 C-10 C-UR4 0 1 50 0 0 0PAμ (7819.4) 27 FC-UR4 3 1 50 1 2 50 C-11 C-UR3 0 1 50 0 0 0 C-12 C-UR40 1 50 0 0 0 PES/Co (2681.4) 30 FC-UR4 3 2 50 2 0 0 C-13 C-UR3 0 0 0 0 00 C-14 C-UR4 0 0 0 0 0 0 Co (1511.1) 31 HFPO-UR4 3 1 70 2 0 60 C-15C-UR3 0 0 0 0 0 0 C-16 C-UR4 0 0 0 0 0 0The results indicated that substrates treated with urethanes made fromthe HFPO oligomer alcohol and triisocyanate had good performance, bothfor oil and water repellency. On the other hand, substrates treated withurethanes made from HFPO oligomer alcohol and diisocyanate had very lowperformance. On PES/Co and Cotton, no oil or water repellency wasobserved.

Examples 32 to 41

In examples 32 to 41 the performance of treated substrates after aircure as well as the performance after extended home launderings wasevaluated. Therefore, cotton samples were treated with FC polyetherurethanes FC-UR5 and FC-UR6, so as to give and add-on level as indicatedin table 6. The samples were evaluated for their oil and waterrepellency, after air cure and after curing at 150° C. during 10minutes. No water repellency was observed after air cure. The otherresults are given in Table 6.

TABLE 6 Ex % Air dry Initial 5 HL 20 HL No FC-UR SOF OR OR SR OR SR ORSR Cotton (IND) 32 FC-UR5 0.2 4.5 5 80 4 60 2 60 33 FC-UR5 0.5 5 6 80 575 4 60 34 FC-UR5 1 6 6 80 5 70 4 60 35 FC-UR6 0.5 3 4 60 2 0 1 0 36FC-UR6 1 4 5 60 4 0 3 0 Cotton (SHIPP) 37 FC-UR5 0.2 4 4.5 75 3 50 2 038 FC-UR5 0.5 5 5 80 5 75 3.5 60 39 FC-UR5 1 5 6 75 5 75 4 5 40 FC-UR60.5 3 4 50 2 50 1 0 41 FC-UR6 1 5 5 60 5 50 3 0 Note: the OR of samples34 and 39 was 3 after 50 HL.As can be seen from the results in table 6, very strong and durable oilrepellency could be achieved on cotton, especially with the lower chainoligomeric urethanes. Furthermore, a remarkably high oil repellency wasnoticed for the air dried samples. High durability of the oil repellencywas observed, even after repeated home launderings.

Examples 42 to 53

In examples 42 to 53 cotton samples were treated with fluorochemicalpolyether urethanes FC-UR7 and FC-UR8, derived from short chain and longchain HFPO oligomers respectively, so as to give and add-on level asindicated in Table 7. The samples were air dried and cured at 150° C.during 10 minutes. The oil and water repellency were measured after airdry, after 150° C. cure and after 5 HL. No water repellency was observedafter air dry or 5 HL. The other results are given in Table 7.

TABLE 7 Cotton substrates treated with FC polyether urethanes Air dryInitial 5 HL Ex FC-UR Substrate % SOF OR OR SR OR 42 FC-UR7 IND 0.2 4 50 / 43 FC-UR7 IND 0.5 5 6 50 5 44 FC-UR7 IND 1 5 6 50 5 45 FC-UR7 SHIPP0.2 4 5 0 / 46 FC-UR7 SHIPP 0.5 5 5 50 5 47 FC-UR7 SHIPP 1 5 5 50 5 48FC-UR8 IND 0.2 2 2 0 / 49 FC-UR8 IND 0.5 5 5 60 3 50 FC-UR8 IND 1 5 5 05 51 FC-UR8 SHIPP 0.2 2.5 2 0 / 52 FC-UR8 SHIPP 0.5 4.5 5 0 4 53 FC-UR8SHIPP 1 5 5 0 5The substrates, treated with the FC polyether urethane had very high anddurable oil repellency.

Examples 54 to 69

In examples 54 to 69, different substrates were treated with FCpolyether urethanes, made with difunctional chain extenders, so as togive 0.3% SOF. After treatment the fabrics were dried at 160° C. during1.5 minutes. The treated substrates were tested for their oil and waterrepellency, initially and after 5 home launderings (ironing). Theresults are summarized in table 8.

TABLE 8 Substrates treated with FC polyether urethanes havingdifunctional chain extenders Ex Initial Bundesmann 5 HL ironing No FC-UROR WR SR 1′ 5′ 10′ % abs OR WR SR PESμ (6145.3) 54 FC-UR9 0.5 2 100 2 21 23 0 1 90 55 FC-UR10 1 2 100 2 2 1 23 0 1 85 56 FC-UR11 1 2 100 3 1 122 0 1 90 57 FC-UR12 2 2 100 2 1 1 29 1 1 90 PAμ (7819.4) 58 FC-UR9 32.5 85 1 1 1 43 2 2 75 59 FC-UR10 3 3 90 1 1 1 34 2 2 75 60 FC-UR11 2 270 / / / / 2 1.5 60 61 FC-UR12 3 2 70 / / / / 2 4.5 60 PES/Co (2681.4)62 FC-UR9 1.5 2 100 2 1 1 31 1 1 85 63 FC-UR10 1 3 90 2 1 1 35 1 1.5 8064 FC-UR11 2 3 95 3 1 1 23 2 2 85 65 FC-UR12 3 2 80 1 1 1 31 2 1 70 Co(1511.1) 66 FC-UR9 2 2 85 / / / / 2 1 70 67 FC-UR10 1 2 90 / / / / 1 280 68 FC-UR11 2 2 85 / / / / 1 1 80 69 FC-UR12 3 2 85 / / / / 1 1 75The results indicated that the incorporation of difunctional chainextenders in the polyurethane resulted in many cases in an improvementof the overall performance of substrates treated therewith. Substrateswith strong initial and also durable dynamic repellency could be made.

Examples 70 to 81

In examples 70 to 81, different substrates were treated with FCpolyether urethane made from HFPO-diol (FC-UR13) or with a 50/50 blendof FC polyether urethanes, as indicated in table 11, so as to give 0.3%SOF. After treatment the fabrics were dried at 160° C. during 1.5minutes. The treated substrates were tested for their oil and waterrepellency, initially and after 5 home launderings (ironing). Theresults are summarized in Table 9.

TABLE 9 Substrates treated with FC polyether urethane blends Ex InitialBundesmann 5 HL ironing No FC-UR OR WR SR 1′ 5′ 10′ % abs OR WR SR PESμ(6145.3) 70 FC-UR13 0 1 100 4.5 4 4 12.2 0 1 85 71 FC-UR10/ 0.5 2 1004.5 4.5 4.5 3.9 0 1 95 FC-UR13 72 FC-UR3/ 2 2 100 3.5 2.5 1 13.4 1 1 90FC-UR13 PAμ (7819.4) 73 FC-UR13 2 2.5 100 5 4 3 11.7 0.5 1.5 90 74FC-UR10/ 2 2 95 3 2 1.5 23.1 1.5 2 75 FC-UR13 75 FC-UR3/ 3 2 75 / / / /2 2 60 FC-UR13 PES/Co (2681.4) 76 FC-UR13 1 1 100 1 1 1 25.9 0 1 80 77FC-UR10/ 2.5 2.5 100 3 2 1 12.4 1 1 80 FC-UR13 78 FC-UR3/ 2.5 2 95 1 1 124.7 2 1 70 FC-UR13 Co (1511.1) 79 FC-UR13 1 2 85 / / / / 0 1 80 80FC-UR10/ 2.5 2 95 1 1 1 37.8 1.5 1 80 FC-UR13 81 FC-UR3/ 3 1 75 / / / /2.5 0 80 FC-UR13The results demonstrated that excellent dynamic water repellency, bothinitial and after homelaundering could be achieved with urethanes madefrom HFPO-oligomer diol. Especially strong results were obtained onsynthetic substrates (PESμ and PAμ). The oil repellency could beincreased using a blend of urethanes made from HFPO-oligomer diol andHFPO-oligomer alcohol.

Examples 82 to 101

In examples 82 to 101, different substrates were treated with FCpolyether urethanes, derived from a mixture of HFPO-oligomer alcohol anddiol, so as to give 0.3% SOF. After treatment the fabrics were dried at160° C. during 1.5 minutes. The treated substrates were tested for theiroil and water repellency, initially and after 5 home launderings(ironing). The results are summarized in Table 10.

TABLE 10 Substrates treated with FC-polyether urethanes, derived frommixture of HFPO-oligomer alcohol and diol. Ex Initial Bundesmann 5 HLironing No FC-UR OR WR SR 1′ 5′ 10′ % abs OR WR SR PESμ (6145.3) 82FC-UR14 0 2 100 4.5 3.5 2.5 13 0 2 80 83 FC-UR15 0 1.5 100 4.5 3.5 2.515.7 0.5 1 80 84 FC-UR16 0 1 100 3 1 1 18.8 0 1 70 85 FC-UR17 1 1.5 1002.5 1.5 1 17.3 0 1 70 86 FC-UR18 1 2 100 3 2 1 15.6 0 1 85 PAμ (7819.4)87 FC-UR14 2 2 70 / / / / 1 1 50 88 FC-UR15 2 3 60 / / / / 1 1.5 60 89FC-UR16 2 2.5 60 / / / / 0 1 60 90 FC-UR17 2 1 60 / / / / 1 1 60 91FC-UR18 3 2 75 / / / / 1.5 3 50 PES/Co (2681.4) 92 FC-UR14 3 2.5 100 1 11 23.8 2 2 80 93 FC-UR15 1.5 3 95 1 1 1 23.9 1 1 80 94 FC-UR16 1.5 1 70/ / / / 0 0.5 60 95 FC-UR17 2 1 70 / / / / 1.5 1 60 96 FC-UR18 2 2 100 11 1 21.7 2 1 70 Co (1511.1) 97 FC-UR14 2 2 90 1 1 1 36.8 1.5 1 80 98FC-UR15 2 2 90 1 1 1 36.5 0 1 80 99 FC-UR16 0 0 70 / / / / 0 0 0 100FC-UR17 2 1 70 / / / / 1 0 50 101 FC-UR18 2 2 85 / / / / 2 1 70The results demonstrated that good water repellency, both initial andafter laundering could be achieved with FC polyether urethanes derivedfrom a mixture of HFPO-alcohol and HFPO-diol.

Examples 102 to 189

In examples 102 to 189, substrates were treated with fluorochemicalpolyether urethanes made from a mixture of HFPO-oligomer alcohols(and/or diol) and short chain fluorochemical alkyl alcohols (and/ordiols). Substrates were treated with the FC polyether urethanes, asindicated in table 11, so as to give 0.3% SOF. After treatment thefabrics were dried at 160° C. during 1.5 minutes. The treated substrateswere tested for their oil and water repellency, initially and after 5home launderings (ironing). The results are summarized in Tables 11 to14.

TABLE 11 PAμ (7819.4) substrates treated with FC polyether urethanesInitial 5 HL Ironing Ex No FC-UR OR WR SR OR SR 102 FC-UR19 2 3 85 1 70103 FC-UR20 2.5 2.5 90 1 70 104 FC-UR21 1 2 75 0 50 105 FC-UR22 2 2.5 850 70 106 FC-UR23 2.5 2.5 75 1 70 107 FC-UR24 3.5 2.5 70 1 50 108 FC-UR252.5 2.5 75 1.5 70 109 FC-UR26 1.5 1 75 0.5 70 110 FC-UR27 1.5 2.5 80 170 111 FC-UR28 1.5 1.5 80 1 50 112 FC-UR29 0.5 1.5 80 0 70 113 FC-UR300.5 1.5 70 1 50 114 FC-UR31 1.5 1.5 70 1 50 115 FC-UR32 0 2 70 0 50 116FC-UR33 2 1.5 70 1.5 60 117 FC-UR34 2 2 7 1.5 50 118 FC-UR35 1.5 1.5 751 60 119 FC-UR36 1.5 1.5 75 0.5 70 120 FC-UR37 2.5 1.5 75 0.5 60 121FC-UR38 1.5 1.5 80 1 60 122 FC-UR39 0.5 2 70 0 60 123 FC-UR40 1.5 1.5 700.5 60

TABLE 12 Co (1511.1) substrate treated with FC polyether urethanesInitial 5 HL Ironing Ex No FC-UR OR WR SR OR SR 124 FC-UR19 3 3 50 0 0125 FC-UR20 2 2 85 1 70 126 FC-UR21 1.5 2 100 1 90 127 FC-UR22 2.5 1.560 1 0 128 FC-UR23 2.5 2 85 2 70 129 FC-UR24 2.5 1 50 1 0 130 FC-UR25 32 90 2 70 131 FC-UR26 3 2 85 1.5 75 132 FC-UR27 2 2 90 1 75 133 FC-UR282 2 80 1.5 70 134 FC-UR29 1 2 85 1 80 135 FC-UR30 2 2 80 0.5 70 136FC-UR31 2 2 80 2 70 137 FC-UR32 0.5 2 90 0 80 138 FC-UR33 3 2 75 2 70139 FC-UR34 3.5 1 75 2 70 140 FC-UR35 2 2 80 2 70 141 FC-UR36 2 2 85 280 142 FC-UR37 2.5 1 80 2 70 143 FC-UR38 2.5 1.5 80 2 70 144 FC-UR39 2 170 1.5 70 145 FC-UR40 2.5 1 70 1.5 70

TABLE 13 PES/Co (2681.4) substrate treated with FC polyether urethanesInitial 5 HL Ironing Ex No FC-UR OR WR SR OR SR 146 FC-UR19 4 3 75 1 0147 FC-UR20 2 2.5 90 1 75 148 FC-UR21 1.5 2.5 100 1 85 149 FC-UR22 3.5 375 1 50 150 FC-UR23 3 2.5 95 2 70 151 FC-UR24 3.5 2.5 70 2 0 152 FC-UR254 2.5 100 1 75 153 FC-UR26 3.5 2.5 100 2 75 154 FC-UR27 3 2.5 100 2 80155 FC-UR28 2.5 2.5 85 1.5 75 156 FC-UR29 2 2.5 90 1 80 157 FC-UR30 2.52 90 1.5 75 158 FC-UR31 2.5 2.5 80 2 70 159 FC-UR32 0.5 2 90 0 75 160FC-UR33 3 2 75 2 50 161 FC-UR34 4 2 75 2.5 70 162 FC-UR35 3 2.5 85 2 70163 FC-UR36 2.5 2 90 2 70 164 FC-UR37 2.5 2 80 2 70 165 FC-UR38 3 2 80 270 166 FC-UR39 2.5 2 75 1.5 70 167 FC-UR40 2.5 2 50 1.5 70

TABLE 14 PESμ (6145.3) substrate treated with FC polyether urethanesInitial 5 HL Ironing Ex No FC-UR OR WR SR OR SR 168 FC-UR19 2 2.5 90 0.585 169 FC-UR20 1.5 2 100 0 85 170 FC-UR21 0 2 100 0 85 171 FC-UR22 1.52.5 100 0.5 80 172 FC-UR23 1 2 100 0 85 173 FC-UR24 2 2.5 80 1 80 174FC-UR25 2 2 90 0.5 80 175 FC-UR26 1.5 2 90 0 80 176 FC-UR27 0.5 2 100 090 177 FC-UR28 1 2 100 0 90 178 FC-UR29 0.5 2 100 0 90 179 FC-UR30 1 290 0 80 180 FC-UR31 1 2 100 0 85 181 FC-UR32 0 1.5 100 0 90 182 FC-UR331.5 2 80 1.5 70 183 FC-UR34 2 2 80 1 75 184 FC-UR35 1 2 100 0 85 185FC-UR36 0.5 2 100 0 85 186 FC-UR37 1.5 2 100 0 85 187 FC-UR38 1.5 2 90 080 188 FC-UR39 1 1.5 80 0 75 189 FC-UR40 1.5 1.5 80 0 75Substrates with high and durable oil and/or water repellency could bemade.

Examples 190 to 195

In examples 190 to 195 cotton samples were treated with fluorochemicalpolyether urethane FC-UR43, so as to give and add-on level as indicatedin Table 15. The samples were cured at 150° C. during 10 minutes. Theoil and water repellency were measured initially and after 10 HL and 20HL. The results are given in Table 15.

TABLE 15 Ex % Initial 10 HL 20 HL No Substrate SOF OR SR OR SR OR SR 190IND 0.2 3 60 1 0 0 0 191 IND 0.5 5 75 4 50 3 50 192 IND 1 5 80 4 50 3 50193 SHIP 0.2 3 60 1 0 0 0 194 SHIP 0.5 5 75 3 50 2 50 195 SHIP 1 5 80 470 3 60Cotton substrates having especially high oil repellency, even afterrepeated home launderings were made. Also good durable water repellencywas noticed.

Examples 196 to 207

In examples 196 to 207 cotton samples were treated with fluorochemicalpolyether urethanes FC-UR41 and FC-UR42, derived from short chain HFPOoligomers and polymeric alcohols, so as to give and add-on level asindicated in Table 16. The samples were air dried and cured at 150° C.during 10 minutes. The oil and water repellency were measured after airdry, after 150° C. cure and after 5 HL. No water repellency was observedafter air dry or 5 HL. Results are given in Table 16.

TABLE 16 Air dry Initial 5 HL Ex FC-UR Substrate % SOF OR OR SR OR 196FC-UR41 IND 0.2 2 3 60 0 197 FC-UR41 IND 0.5 4 5 95 2 198 FC-UR41 IND 15 5 95 3 199 FC-UR41 SHIPP 0.2 2 3 60 0 200 FC-UR41 SHIPP 0.5 5 4 90 2.5201 FC-UR41 SHIPP 1 5 4.5 90 4 202 FC-UR42 IND 0.2 / 2 0 0 203 FC-UR42IND 0.5 / 5 70 2 204 FC-UR42 IND 1 / 5 100 4 205 FC-UR42 SHIPP 0.2 / 260 0 206 FC-UR42 SHIPP 0.5 / 5 70 2.5 207 FC-UR42 SHIPP 1 / 5 80 4Cotton substrates having high oil and water repellency were obtained.

Examples 208 and 209 and Comparative Examples C-17 and C-18

In example 208 and 209, polyamide carpet samples were treated with anemulsion containing 0.6% FC polyether urethane FC-UR4 (emulsified withSERMUL™ EA266), by spray application, to give 30% WPU. The carpetsamples were dried at 120° C. during 15-20 min. Comparative examplesC-17 and C-18 were untreated polyamide carpet samples. Oil repellency(OR), water repellency (WR) and Accelerated Dry Soil (ADS) were measuredand are report in Table 17.

TABLE 17 Carpet treated with FC polyether urethane Ex No Carpet FC-UR4WR OR ADS 208 NS1 0.6% solids; 30% WPU 3 4 3 209 NS2 0.6% solids; 30%WPU 2 1.5 3 C-17 NS1 / 0 0 1.5 C-18 NS2 / 0 0 2As can be seen from the results, a considerable improvement ofrepellency properties and soil resistance were observed when the carpetsamples were treated with a composition according to the invention.

Examples 210 to 215

In examples 210 to 215 cotton and polyester/cotton samples were treatedwith fluorochemical polyether urethane FC-UR46, so as to give an add-onlevel as indicated in table 18. The samples were cured at 150° C. during10 minutes. The oil and water repellency were measured initially andafter 10 HL, 20 HL, 30 HL, 40 HL and 50 HL. The results are given inTable 18.

TABLE 18 Initial Initial 10 HL 10 HL 20 HL 20 HL 30 HL 30 HL 40 HL 40 HL50 HL 50 HL Example Substrate % SOF OR SR OR SR OR SR OR SR OR SR OR SR210 SHIPP 0.2 1.75 85 1 80 0 80 / / / / / / 211 SHIPP 0.5 5 100 4 100 3100 2 100 2 100 2 78 212 SHIPP 1.0 5 100 4.25 100 4 95 3 100 3 100 3 95213 Reeve 0.2 1 80 0 75 0 70 / / / / / / 214 Reeve 0.5 5 100 2 100 1.395 1 95 1 95 1 80 215 Reeve 1.0 4.25 100 3 100 2 100 2 100 2 90 2 95

Examples 216 to 217

In examples 216 to 217 cotton and polyester/cotton samples were treatedwith fluorochemical polyether urethane FC-UR47, so as to give an add-onlevel as indicated in table 19. The samples were cured at 150° C. during10 minutes. The oil repellency was measured initially and after 10 HL.The results are given in Table 19.

TABLE 19 Example (with FC-UR47) Substrate % SOF Initial OR 10 HL OR 216SHIPP 0.5 4 3 1.0 5 5 217 Reeve 0.5 4 2.5 1.0 5 4

Examples 218 to 219

In examples 218 to 219 cotton and polyester/cotton samples were treatedwith fluorochemical polyether urethane FC-UR47, so as to give an add-onlevel as indicated in table 20. The samples were cured at 150° C. during10 minutes. The stain release (K, E, and C) was measured initially andafter 20 HL. The results are given in table 20.

TABLE 20 Example (with FC- Initial 20 HL UR47) Substrate % SOF K E C K EC 218 SHIPP 0.5 7.5 7.5 4 8 8 5.5 219 Reeve 0.5 6 5 4 6 6 5

Examples 220 to 231

In Examples 220 to 231 cotton and poly/cotton samples were treated withfluorochemical polyether urethane FC-UR44 or FC-UR45, so as to give anadd-on level as indicated in table 21. The samples were cured at 150° C.during 10 minutes. Oil and water repellency data was measured initially,after 30 HL and after 50 HL. The results are given in table 21.

TABLE 21 Initial 30 HL 50 HL Example FC-UR Substrate % SOF OR SR OR SROR SR 220 FC-UR44 SHIPP 0.2 2 50 0 0 / / 221 FC-UR44 SHIPP 0.5 4 60 2 01 0 222 FC-UR44 SHIPP 1.0 5 75 2.25 60 2 0 223 FC-UR44 Reeve 0.2 1.75 700 50 / / 224 FC-UR44 Reeve 0.5 4 70 1.50 60 2 70 225 FC-UR44 Reeve 1.0 475 2.5 75 2 70 226 FC-UR45 SHIPP 0.2 4 50 0 0 0 0 227 FC-UR45 SHIPP 0.55 60 4 0 3 0 228 FC-UR45 SHIPP 1.0 5 60 5 50 4.25 0 229 FC-UR45 Reeve0.2 3 72.5 1 60 0 0 230 FC-UR45 Reeve 0.5 4.5 70 2.5 60 2 0 231 FC-UR45Reeve 1.0 4.5 80 3 80 2.5 77.5

Examples 232 and 233

In Examples 232 and 233 cotton and poly/cotton samples were treated withfluorochemical polyether urethane FC-UR48, so as to give an add-on levelas indicated in table 22. The samples were cured at 150° C. during 10minutes. The stain release (K, E, and C) was measured initially, after10 HL and after 30 HL. The results are given in Table 22.

TABLE 22 Initial 10 HL 30 HL Ex Substrate % SOF OR K E C OR K E C OR K EC 232 SHIPP 0.5 4 7 7 5 3 7 6.5 4.5 1 6.5 7 5 233 Reeve 0.5 5 6 6 4 4.756.5 5 5 3 6 6 5Preparation of FC-UR49; Fluorochemical Urethane MeFBSE/N3300/PEG1450/APTES

A 1 liter flask was charged with MeFBSE (58.89 g), DBTDL (3 drops; ˜20mg) and MIBK(237.0 g). The temperature of the stirred mixture was raisedto 60° C. under a purge of dry nitrogen. DES N3300 (40.0 g) was thenslowly added, maintaining the temperature between 60-65° C. Uponcompletion of the addition, the reaction mixture was stirred for 1 hourat 60° C. APTES (3.42 g) was then added dropwise, keeping thetemperature of the reaction mixture below 65° C. The reaction mixturewas stirred for 30 minutes. Solid PEG 1450 (18.69 g) was added to thestirred mixture, and the reaction was followed to completion via FTIR,as determined by disappearance of the —NCO band at approximately 2289wavenumbers.

Emulsification: To this vigorously stirred organic mixture was slowlyadded deionized water (944 g; at 60° C.). This pre-emulsion mixture wasthen sonicated for 2 minutes. A rotary evaporator connected to anaspirator was used to strip the MIBK from the mixture. The resultingemulsion was 20-30% solids.

Examples 234 and 239 and Comparative Examples C-19 to C-30

TABLE 23 Initial Intial Intial Ex Substrate % FC-UR49 % FC-UR48 Spray ORC 234 SHIPP 0.25 0.25 75 3 4 235 SHIPP 0.50 0.50 70 5 5 236 K-2 0.250.25 80− 7 7 237 K-2 0.50 0.50 75 7 7 238 TCIK 1.0 1.0 — 5 6 239 TCTK1.0 1.0 — 5 6 C-19 SHIPP 0.50 — 60 1 6.5 C-20 SHIPP — 0.50 50 4 3 C-21SHIPP 1.0 — 75 5 7 C-22 SHIPP — 1.0 75 5 4 C-23 K-2 0.50 — 80 7 7 C-24K-2 — 0.50 75 5 4 C-25 K-2 1.0 — 80+ 7 7.5 C-26 K-2 — 1.0 80− 7 3 C-27TCIK 2.0 — — 5 7 C-28 TCIK — 2.0 5 3 C-29 TCTK 2.0 — — 5 6.5 C-30 TCTK —2.0 — 5 5The data listed in Table 23 demonstrates the improvement in Stain C(particulate oily stain release) by addition of FC-UR49 to theformulations, with little or no resultant negative effect on therepellent attributes.

1. Fluorochemical composition comprising a dispersion or a solution of(A) a fluorinated repellent compound, wherein said fluorinated compoundcomprises the reaction product of: (i) a fluorinated polyether accordingto the formula:R¹ _(f)—O—[CF(CF₃)—CF₂O]_(n)—CF(CF₃)-A-Q¹-T_(k) wherein R¹ _(f)represents a perfluorinated alkyl group, n is an integer of 3 to 25, Ais a carbonyl group or CH₂, Q¹ is a chemical bond or an organic divalentor trivalent linking group and T represents a functional group capableof reacting with an isocyanate and k is 1 or 2, wherein theperfluorinated polyether group has a weight average molecular weight ofat least 750 g/mol to about 100,000 g/mol; (ii) an isocyanate componentselected from a polyisocyanate compound that has at least 3 isocyanategroups or a mixture of polyisocyanate compounds wherein the averagenumber of isocyanate groups per molecule is more than 2; (iii) anon-fluorinated oxime blocking agent; and (iv) optionally one or moreco-reactants capable of reacting with an isocyanate group selected fromthe group consisting of water, monofunctional alcohols, diols andperfluoroaliphatic compounds of the formula:(R_(f) ⁴)_(x)-L-Y, wherein R_(f) ⁴ represents a perfluoroaliphatic grouphaving 3 to 6 carbon atoms, L represents a non-fluorinated organicdivalent or multi-valent linking group, Y represents anisocyanate-reactive functional group and x is an integer of 1 to 20, and(B) a fluorochemical stain release compound.
 2. Fluorochemicalcomposition according to claim 1 wherein T is selected from the groupconsisting of hydroxy and amino groups.
 3. Fluorochemical compositionaccording to claim 1 wherein said reaction product is obtained byreacting between 5 and 100 mole % of the isocyanate groups of theisocyanate component have been reacted with said fluorinated polyetherof formula (I) and wherein the remainder of the isocyanate groups hasbeen reacted with a said one or more coreactants.
 4. The composition ofclaim 1 wherein said component (B) comprises one or more urethaneoligomers of at least two repeating units selected from the groupconsisting of fluorine-containing urethane oligomers and long-chainhydrocarbon-containing urethane oligomers, wherein said oligomerscomprise the reaction product of: (a) one or more polyfunctionalisocyanate compounds; (b) one or more polyols; (c) one or moremonoalcohols selected from the group consisting of fluorocarbonmonoalcohols, optionally substituted long-chain hydrocarbonmonoalcohols, and mixtures thereof; (d) one or more silanes of thefollowing formula:X—R¹¹—Si—(Y)₃ wherein X is —NH₂; —SH; —OH; —N═C═O; or —NRH where R isselected from the group consisting of phenyl, straight and branchedaliphatic, alicyclic, and aliphatic ester groups; R¹ is an alkylene.heteroalkylene, aralkylene, or heteroaralkylene group; and each Y isindependently a hydroxyl; a hydrolyzable moiety selected from the groupconsisting of alkoxy, acyloxy, heteroalkyoxy, heteroacyloxy, halo, andoxime; or a non-hydrolyzable moiety selected from the group consistingof phenyl, alicyclic, straight-chain aliphatic, and branched-chainaliphatic, wherein at least one Y is a hydrolyzable moiety; andoptionally (e) one or more water-solubilizing compounds comprising oneor more water-solubilizing groups and at least one isocyanate-reactivehydrogen containing group.
 5. The chemical composition of claim 4wherein the diol is selected from the group consisting of a branched- orstraight-chain hydrocarbon diol, a diol containing at least onesolubilizing group, a fluorinated diol comprising a monovalent ordivalent perfluorinated group, a diol comprising a silane group, apolyalkylsiloxane diol, a polyarylsiloxane diol, and mixtures thereof.6. The chemical composition of claim 4 wherein the fluorocarbonmonoalcohol is a compound of the following formula:R_(f) ¹⁰-Z-R¹²—OH wherein: R_(f) ¹⁰ is a perfluoroalkyl group or apertluoroheteroalkyl group; Z is a connecting group selected from acovalent bond, a sulfonamido group, a carboxamido group, a carboxylgroup, or a sulfinyl group; and R¹² is a divalent straight- orbranched-chain alkylene, cycloalkylene, or heteroalkylene group of 1 to14 carbon atoms.
 7. The chemical composition of claim 6 wherein R_(f) ¹⁰is a perfluoroalkyl group of 2 to 6 carbons.
 8. The chemical compositionof claim 4 wherein component (B) comprises the reaction product of: oneor more polyfunctional isocyanate compounds and one or more polyolshaving a molar ratio of from about 1:0.25 to about 1:0.45; one or morepolyfunctional isocyanatc compounds and one or more monoalcohols havinga molar ratio of from about 1:0.30 to about 1:0.60; one or morepolyfunctional isocyanate compounds and one or more silanies, of formula(I), having a molar ratio of from about 1:0.001 to about 1:0.15; and oneor more polyfunctional isocyanate compounds and one or morewater-solubilizing compounds having a molar ratio of from about 1:0 toabout 1:1.6.
 9. A coating composition comprising a solution comprisingthe chemical composition of claim 1 and a solvent.
 10. Fluorochemicalcomposition according to claim 1 wherein said fluorinated compounds (A)and (B) are dispersed in water or an organic solvent.
 11. Fluorochemicalcomposition according to claim 1 wherein said fluorinated compounds (A)and (B) are dispersed in water and wherein the aqueous dispersioncontains a surfactant.
 12. Fluorochemical composition according to claim1 wherein the amount of fluorinated compounds (A) and (B) in thecomposition is between 0.1% by weight and 10% by weight.
 13. Method oftreatment of a fibrous substrate, comprising applying to the fibroussubstrate a fluorochemical composition of claim
 1. 14. Method accordingto claim 13 wherein the amount of the fluorochemical composition appliedis such that the amount of fluorinated compounds (A) and (B) is between0.2% by weight and 3% by weight relative tothe weight of the fibroussubstrate.
 15. Fluorochemical composition according to claim 1 whereinsaid reaction product is obtained by reacting betwcen 10 to 30% of theisocyanate groups of the isocyanate component with the perfluorinatedpolyether compound according to formula (I), between 90 and 30% of theisocyanate groups with a non-fluorinated oxime blocking agent and theremainder of the isocyanate groups of the isocyanate component isreacted with one or more of said co-reactants.